All-inorganic solvents for electrolytes

Information

  • Patent Grant
  • 10707526
  • Patent Number
    10,707,526
  • Date Filed
    Monday, March 28, 2016
    8 years ago
  • Date Issued
    Tuesday, July 7, 2020
    4 years ago
Abstract
An all-inorganic electrolyte formulation for use in a lithium ion battery system comprising at least one of each a phosphoranimine, a phosphazene, a monomeric organophosphate and a supporting lithium salt. The electrolyte preferably has a melting point below 0° C., and a vapor pressure of combustible components at 60.6° C. sufficiently low to not produce a combustible mixture in air, e.g., less than 40 mmHg at 30° C. The phosphoranimine, phosphazene, and monomeric phosphorus compound preferably do not have any direct halogen-phosphorus bonds. A solid electrolyte interface layer formed by the electrolyte with an electrode is preferably thermally stable ≥80° C.
Description
FIELD OF THE INVENTION

The present invention relates to a solvent system comprising a mixture of primary solvent phosphoranimine (PA) derivatives, and co-solvents comprised of cyclotriphosphazene (Pz) derivatives optionally with monomeric phosphorus (MP) compound additives, for the potentially complete replacement of organic solvents in an electrolyte formulation. A preferred application is in lithium ion batteries.


BACKGROUND OF THE INVENTION

Batteries with high activity metals, i.e., cell potentials above about 1.5 V, are subject to hydrolysis of aqueous electrolytes. Therefore, rechargeable high energy batteries typically employ non-aqueous electrolytes which lack free hydroxyl substituents. Other criteria for suitable electrolytes are solubility for a supporting salt which yields a charge carrier ion in sufficient concentration to permit high current density, while avoiding strongly bound complexes of the charge carrier ion with the solvent, and a sufficiently low viscosity to permit efficient charge carrier transport through the electrolyte. Further, the battery typically has a storage temperature range of 0° C. or below to 60° C. or above, and the electrolyte should be reasonably stable as a liquid within that range. Finally, the electrolyte should be chemically inert with respect to the battery chemistry, with the exception of the formation of a stable solid electrolyte interphase (SEI) layer near the reactive surface of the electrode, which permits flow of the charge carrier ions between the bulk electrolyte solution and the electrode surfaces, while protecting the bulk electrolyte solution from large-scale decomposition by the electrochemical reactions that during cycling. The SEI should be dynamic, and reform as required under normal battery cycling conditions from the bulk electrolyte solution.


Lithium ion batteries have been in widespread use for decades. These energy storage systems have been investigated for a wide variety of applications, from small single cell platforms, such as watches, phones and the like; to larger format platforms such as those applicable for transportation systems and potentially grid-scale energy storage. A considerable limitation of lithium ion batteries containing lithium salts in organic solvents, such as ethylene carbonate and ethyl methyl carbonate, is the potential for the ignition of the flammable electrolyte solution under certain operating conditions. Also notable is the degradation of the solvent and the formation of the SEI under current draw that can raise the temperature and hence the internal pressure generated causing the battery cell to rupture. Multiple approaches to effect the replacement of organic solvents from battery electrolytes have been investigated over the past 20+ years. Some have limiting requirements that make them impractical for wide-scale adoption for common multi-cell applications, such as thermal requirements (molten salts) and complex engineering designs (flow batteries). There is a pressing need for a complete replacement of current organic electrolyte systems without these constraints. One area that has shown promise of fulfilling these stringent requirements is through the use of phosphorus-based inorganic compounds. The present invention leverages compounds of this nature to achieve the goal of eliminating all organic components from the electrolyte system for a wide variety of lithium ion-based energy storage platforms.


Most of the commercial electrolytes for lithium-ion batteries are LiPF6 dissolved in a mixture of organic carbonate and/or ester solvents. These electrolyte blends are highly volatile and highly flammable, with typical flash points as low as 30° C. or less. This presents serious safety concerns especially when utilized in large format cells or when the cells come under undo stress or physical damage. One approach to improve the safety performance of the electrolyte is to use additives and co-solvents to reduce the flammability of the organic carbonate and ester electrolytes. A variety of additives and co-solvents have been proposed, including sulfones, ionic liquids, phosphates, phospholanes, Pzs, siloxanes, fluorinated carbonates, and fluorinated ethers and mixtures thereof. In addition to flammability suppression, additives have also been used to improve SEI formation, overcharge protection, and thermal stability.


Electrolyte solutions used in lithium-ion batteries are known to be unstable at high temperatures and high voltages. Over time, the organic electrolyte solution turns into a tar-like material at high temperatures. The electrolyte solutions may include carbonate-based solvents, such as dimethyl carbonate (DMC), ethylene carbonate (EC), ethylmethyl carbonate (EMC), etc. However, the carbonate-based solvents are problematic due to their high volatility, flammability, and decomposition at even modestly elevated temperatures, such as low as 60° C.


The lithium metal anode provides a very high capacity and the lowest potential of all metallic anode materials. Therefore, it is not only used in commercial primary lithium metal batteries, but is also proposed as an anode material in rechargeable lithium/air and lithium/sulfur batteries, which are considered as super-high specific energy accumulators of tomorrow. These high energy batteries are urgently demanded to meet a longer driving range in electric vehicles (electro-mobility). However, the rechargeable lithium metal anode suffers from poor rechargeability and low safety. Due to the low potential, the electrolytes traditionally used are thermodynamically not stable against lithium. Their reductive decomposition and the parallel corrosion of the Li electrode lead to the formation of the SEI. This passivating film is supposed to slow down or in the ideal case even prevent electrolyte decomposition. In addition, heterogeneous lithium deposition and dissolution during charge and discharge of the lithium metal anode eventually leads to high surface area lithium, commonly called lithium dendrites in most of the organic solvent-based electrolytes. This may cause a loss of active material due to enhanced lithium corrosion at the high surface area Li, as well as due to the disconnection of dendrites from electronic contact. In addition, short-circuit of the cell may happen when the dendrites grow across the electrolyte to the cathode. In any case, the continuous creation of new lithium surfaces by dendrite formation leads to continuous electrolyte decomposition during cycling.


Overpotentials are generated by kinetic hindrances in the system. In lithium plating and stripping processes, these may include the lithium ion transport in the electrolyte and in the electrode/electrolyte interphase, such as the SEI, and always the kinetic hindrance of the lithium ion reduction and oxidation processes at the electrode itself, influencing the charge transfer resistance.


To reduce the flammability of the electrolyte solution, organophosphorus compounds, such as phosphates and cyclic Pzs, have been investigated as an additive or co-solvent to the electrolyte solution. PA compounds, which include a phosphorus-nitrogen double bond, and additional substituents on the phosphorus and nitrogen, are known in the art as synthetic intermediates in the formation of polyphosphazene compounds or cyclic Pz compounds. PA compounds have been disclosed for use in positive electrodes of lithium primary cells and for use in electrolyte solutions in combination with an aprotic organic solvent. See Wu et al., “An Electrochemically Compatible and Flame-Retardant Electrolyte Additive for Safe Lithium Ion Batteries”, J. Power Sources 227 (2013) 106-110, expressly incorporated herein by reference in its entirety, which discusses a phosphazenic compound as an electrolyte additive. The phosphazenic compound was triethoxyphosphazen-N-phosphoryldiethylester (PNP), which included a phosphine oxide functional group bonded to a nitrogen atom of the phosphazenic compound. The electrochemical characterization of the PNP-containing electrolyte was tested in MCMB/Li half-cells at 0% loading, 10% loading, 20% loading, 50% loading, and pure PNP, showing a 20% decrease in capacity at 20% loading. At 10% loading, there was little observed difference when compared to traditional electrolytes. However, loadings in excess of 20%, for example, at 50% and 100%, were not able to cycle effectively.


US 2015340739 (Klaehn et al.), expressly incorporated herein by reference in its entirety, discloses an electrolyte solution comprising at least one PA compound and a metal salt. The at least one PA compound comprises a compound of the chemical structure X—N═P(R1,R2,R3), where X is an organosilyl group (e.g., trimethyl silyl), an alkyl group, or an aryl group (e.g., a tert-butyl group) and each of R1, R2, and R3 is independently selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, or a sulfur or nitrogen analogue thereof. The PA compound is an acyclic (e.g., linear) compound that includes a double bond between a phosphorus atom and a nitrogen atom of the PA compound. Three pendant groups are bonded to the phosphorus atom, and a pendant group is bonded to the nitrogen atom. The PA compound is a monomeric Pz compound. A cationic pendant group may also be used as at least one of R1, R2, and R3. The choice of functional group (X) bonded to the nitrogen atom may be more limited by synthetic chemistry techniques than is the choice of functional group bonded to the phosphorus atom. The pendant groups on each of the phosphorus atom and the nitrogen atom may be the same as, or different from, one another. The PA compound should not include a halogen directly bonded to the phosphorus for stability. However, a halogen may otherwise be a substituent.


See, U.S. Pat. Nos. 4,248,868; 4,613,676; 4,719,288; 4,722,877; 4,727,060; 4,772,433; 4,810,599; 4,828,945; 4,863,903; 4,931,591; 4,985,317; 5,041,346; 5,061,581; 5,110,694; 5,114,809; 5,153,080; 5,153,082; 5,176,969; 5,180,645; 5,188,783; 5,190,695; 5,337,184; 5,420,000; 5,426,005; 5,443,601; 5,474,860; 5,548,055; 5,567,783; 5,576,120; 5,591,545; 5,633,098; 5,660,948; 5,672,446; 5,672,465; 5,698,338; 5,700,298; 5,707,760; 5,725,968; 5,728,489; 5,731,104; 5,744,264; 5,753,388; 5,756,231; 5,780,182; 5,783,333; 5,786,110; 5,789,110; 5,824,434; 5,843,592; 5,851,504; 5,912,093; 5,962,169; 5,998,559; 6,007,947; 6,013,393; 6,015,638; 6,087,426; 6,096,453; 6,103,419; 6,103,426; 6,168,885; 6,207,326; 6,316,149; 6,379,842; 6,391,492; 6,395,423; 6,413,675; 6,413,676; 6,416,905; 6,444,370; 6,447,952; 6,472,104; 6,475,679; 6,475,680; 6,492,449; 6,599,664; 6,605,237; 6,645,675; 6,664,006; 6,699,623; 6,721,168; 6,759,164; 6,759,460; 6,797,019; 6,815,119; 6,828,065; 6,841,301; 6,893,774; 6,908,186; 6,955,867; 7,005,206; 7,008,564; 7,052,805; 7,060,744; 7,067,219; 7,077,516; 7,081,320; 7,084,290; 7,091,266; 7,094,501; 7,099,142; 7,118,694; 7,226,702; 7,229,719; 7,238,450; 7,247,740; 7,273,597; 7,285,362; 7,316,855; 7,378,193; 7,410,731; 7,429,433; 7,473,491; 7,494,745; 7,498,102; 7,524,439; 7,557,637; 7,560,595; 7,579,118; 7,582,380; 7,585,587; 7,585,994; 7,588,859; 7,598,002; 7,656,125; 7,678,505; 7,695,860; 7,695,862; 7,713,449; 7,718,321; 7,718,826; 7,759,418; 7,781,105; 7,811,707; 7,811,708; 7,820,328; 7,824,800; 7,828,728; 7,838,143; 7,851,090; 7,875,204; 7,875,393; 7,939,199; 7,939,206; 7,951,495; 7,976,983; 7,977,393; 7,989,109; 8,000,084; 8,003,241; 8,003,256; 8,012,615; 8,030,500; 8,034,491; 8,048,569; 8,062,796; 8,071,233; 8,076,031; 8,076,032; 8,084,998; 8,092,940; 8,119,038; 8,124,269; 8,133,614; 8,137,844; 8,153,307; 8,168,330; 8,168,831; 8,178,009; 8,187,749; 8,211,336; 8,221,915; 8,227,103; 8,236,449; 8,257,866; 8,257,870; 8,263,697; 8,268,197; 8,287,483; 8,301,322; 8,308,971; 8,309,240; 8,357,450; 8,367,755; 8,377,596; 8,384,058; 8,415,045; 8,420,266; 8,450,012; 8,455,141; 8,465,871; 8,470,472; 8,486,560; 8,486,565; 8,512,896; 8,512,899; 8,524,399; 8,556,996; 8,562,873; 8,574,773; 8,579,994; 8,592,081; 8,597,815; 8,597,827; 8,628,873; 8,652,688; 8,658,062; 8,669,114; 8,673,499; 8,679,670; 8,679,684; 8,686,074; 8,703,310; 8,703,344; 8,715,863; 8,728,170; 8,734,668; 8,734,674; 8,734,988; 8,741,486; 8,754,138; 8,765,295; 8,778,533; 8,785,022; 8,795,886; 8,795,903; 8,801,810; 8,802,285; 8,814,956; 8,815,432; 8,822,084; 8,822,088; 8,828,605; 8,841,035; 8,845,764; 8,846,249; 8,846,251; 8,846,922; 8,852,801; 8,852,813; 8,870,810; 8,871,385; 8,889,301; 8,900,754; 8,906,549; 8,922,959; 8,927,127; 8,945,774; 8,974,947; 8,986,881; 8,999,009; 9,012,093; 9,012,094; 9,077,037; 9,077,046; 9,093,716; 9,099,252; 9,099,756; 9,105,908; 9,105,942; 9,111,684; 9,112,212; 9,118,088; 9,123,973; 9,130,214; 9,130,245; 9,142,357; 9,147,906; 9,166,206; 9,166,222; 9,166,249; 9,172,076; 9,172,088; 9,172,094; 9,183,995; 9,184,467; 9,184,468; 9,190,616; 9,190,695; 9,190,698; 9,196,926; 9,203,084; 9,203,107; 9,203,113; 9,206,210; 9,207,513; 9,209,456; 9,214,659; 9,219,274; 9,227,850; 9,230,746; 9,231,243; 9,236,634; 9,236,635; 9,240,614; 9,246,150; 9,252,399; 9,257,720; 9,263,731; 9,263,764; 9,273,399; 9,281,541; 9,281,543; 9,284,324; 9,287,560; 9,293,749; 9,293,787; 9,293,796; RE37076; 20010004506; 20010004507; 20010012590; 20020014616; 20020031701; 20020039275; 20020048706; 20020055047; 20020076611; 20020085968; 20020090331; 20020090547; 20020094311; 20020098135; 20020100725; 20020102196; 20020110739; 20020122979; 20020127162; 20020127169; 20020127454; 20020128364; 20020136681; 20020136683; 20020150524; 20020155353; 20020159943; 20020160270; 20020182488; 20020185627; 20020193533; 20020197522; 20020197531; 20030003369; 20030059683; 20030068555; 20030091904; 20030108801; 20030113635; 20030125437; 20030129500; 20030148191; 20030170548; 20030175597; 20030175598; 20030190531; 20030198868; 20040009404; 20040013927; 20040039134; 20040053138; 20040085710; 20040126305; 20040126658; 20040126659; 20040139587; 20040142246; 20040146778; 20040146786; 20040151985; 20040157122; 20040158091; 20040170901; 20040189762; 20040189763; 20040191635; 20040192853; 20040220348; 20050008938; 20050042503; 20050085655; 20050095197; 20050095504; 20050106458; 20050106460; 20050123836; 20050136329; 20050153207; 20050158626; 20050164093; 20050175529; 20050175904; 20050181280; 20050214700; 20050215764; 20050221168; 20050228087; 20050249656; 20050249667; 20050255385; 20050260120; 20050272214; 20060032046; 20060034943; 20060035137; 20060046151; 20060073381; 20060121355; 20060147371; 20060147807; 20060154144; 20060154147; 20060166098; 20060172200; 20060180796; 20060194119; 20060204856; 20060210873; 20060210883; 20060217568; 20060269834; 20060281010; 20060281011; 20060292451; 20070020529; 20070026315; 20070027129; 20070029972; 20070037046; 20070037063; 20070040154; 20070043158; 20070048209; 20070048596; 20070048622; 20070048623; 20070054180; 20070077496; 20070092549; 20070117007; 20070141470; 20070149496; 20070166617; 20070172740; 20070180688; 20070182418; 20070183954; 20070207384; 20070212615; 20070216469; 20070243470; 20070298314; 20080008928; 20080008933; 20080020276; 20080020285; 20080044736; 20080051495; 20080063585; 20080063588; 20080075999; 20080089830; 20080096056; 20080099734; 20080107586; 20080118428; 20080118843; 20080119421; 20080138700; 20080152996; 20080153005; 20080160417; 20080164444; 20080171268; 20080176141; 20080193840; 20080193848; 20080213588; 20080213661; 20080224100; 20080233477; 20080241693; 20080241699; 20080254361; 20080261116; 20080269492; 20080311025; 20090004094; 20090005824; 20090011340; 20090017364; 20090023071; 20090027827; 20090029138; 20090029193; 20090035656; 20090075176; 20090081547; 20090081548; 20090104523; 20090123813; 20090130567; 20090136854; 20090155696; 20090155697; 20090169463; 20090181296; 20090186267; 20090191464; 20090208835; 20090246625; 20090246628; 20090253035; 20090253046; 20090256528; 20090259420; 20090269654; 20090269673; 20090280400; 20090291330; 20090297937; 20090305016; 20090311587; 20100009260; 20100015521; 20100018034; 20100047695; 20100062345; 20100068461; 20100068605; 20100075222; 20100075225; 20100078599; 20100086823; 20100090650; 20100119881; 20100119956; 20100124691; 20100125082; 20100125087; 20100136410; 20100143770; 20100159346; 20100164436; 20100167121; 20100173139; 20100178555; 20100183917; 20100190059; 20100200403; 20100209782; 20100216016; 20100216027; 20100224824; 20100233523; 20100240813; 20100255356; 20100279155; 20100285352; 20100285354; 20100285358; 20100285373; 20100297502; 20100299008; 20100304205; 20100304223; 20100310941; 20100323238; 20100330410; 20100330419; 20100330421; 20100330423; 20100330425; 20110014527; 20110020704; 20110020706; 20110024396; 20110027656; 20110033734; 20110033756; 20110039157; 20110049745; 20110052966; 20110059349; 20110067230; 20110070495; 20110070504; 20110077880; 20110081563; 20110081581; 20110086781; 20110097628; 20110097630; 20110098463; 20110104553; 20110104565; 20110111294; 20110111304; 20110117407; 20110117445; 20110117446; 20110123869; 20110136019; 20110143201; 20110143219; 20110159329; 20110159365; 20110159377; 20110159379; 20110171502; 20110177393; 20110181249; 20110183216; 20110189512; 20110189520; 20110189548; 20110189579; 20110195318; 20110200874; 20110206979; 20110206994; 20110207000; 20110229761; 20110236751; 20110236765; 20110250503; 20110256457; 20110264381; 20110274977; 20110287316; 20110287318; 20110293997; 20110301931; 20110305949; 20110305958; 20110319426; 20120003514; 20120003518; 20120007560; 20120015249; 20120021286; 20120028105; 20120034512; 20120045670; 20120052401; 20120058377; 20120060360; 20120064396; 20120070741; 20120077076; 20120077082; 20120082873; 20120082890; 20120082902; 20120082903; 20120088155; 20120088162; 20120094178; 20120100438; 20120105007; 20120107680; 20120107697; 20120107726; 20120115018; 20120121974; 20120121989; 20120121991; 20120129019; 20120129046; 20120133341; 20120135312; 20120141864; 20120141866; 20120141867; 20120141869; 20120141878; 20120141883; 20120141884; 20120148922; 20120155507; 20120164519; 20120164541; 20120169297; 20120171536; 20120171542; 20120175552; 20120177995; 20120183842; 20120183843; 20120183856; 20120183865; 20120183866; 20120188086; 20120189920; 20120202112; 20120208087; 20120218683; 20120219865; 20120225331; 20120225358; 20120225359; 20120231308; 20120231325; 20120231352; 20120244391; 20120244417; 20120251886; 20120251892; 20120273737; 20120276445; 20120288750; 20120288751; 20120288769; 20120289887; 20120293916; 20120295155; 20120295165; 20120301789; 20120301797; 20120308894; 20120315535; 20120315549; 20120321959; 20120328942; 20120328952; 20130004839; 20130004862; 20130011728; 20130011736; 20130017443; 20130017453; 20130022863; 20130022880; 20130026409; 20130040203; 20130043843; 20130048923; 20130052528; 20130052542; 20130055559; 20130059172; 20130065122; 20130065130; 20130069601; 20130069658; 20130069661; 20130071733; 20130071739; 20130071762; 20130072154; 20130078525; 20130084495; 20130084496; 20130084501; 20130088204; 20130089793; 20130090900; 20130092866; 20130095351; 20130095392; 20130100563; 20130108899; 20130108930; 20130115520; 20130115529; 20130130069; 20130130121; 20130130128; 20130135110; 20130136981; 20130143090; 20130143129; 20130149567; 20130149602; 20130149605; 20130157147; 20130157149; 20130157152; 20130163148; 20130164611; 20130164612; 20130169238; 20130171340; 20130171502; 20130171512; 20130177814; 20130183579; 20130183580; 20130189575; 20130189579; 20130195805; 20130196223; 20130196235; 20130199936; 20130202920; 20130202955; 20130202956; 20130202959; 20130202967; 20130202973; 20130209860; 20130209869; 20130209870; 20130209887; 20130209897; 20130216899; 20130216907; 20130216908; 20130216918; 20130216920; 20130224576; 20130224583; 20130230772; 20130230773; 20130230779; 20130232772; 20130234074; 20130236750; 20130236766; 20130244102; 20130244107; 20130252090; 20130252101; 20130260222; 20130260229; 20130260232; 20130260254; 20130260255; 20130264999; 20130266827; 20130266846; 20130266858; 20130266866; 20130271089; 20130277599; 20130280592; 20130280621; 20130288084; 20130288113; 20130288120; 20130288138; 20130295439; 20130295461; 20130295465; 20130295492; 20130302650; 20130302679; 20130302697; 20130302702; 20130309527; 20130309549; 20130309564; 20130309571; 20130316248; 20130319870; 20130320582; 20130323585; 20130323595; 20130323605; 20130327648; 20130330609; 20130330637; 20130337304; 20130337335; 20130337338; 20130337339; 20130337340; 20130337341; 20130337343; 20130337346; 20130344360; 20130344383; 20130344391; 20130344392; 20140011081; 20140011088; 20140015160; 20140017549; 20140017559; 20140017568; 20140017573; 20140023932; 20140023934; 20140030609; 20140030610; 20140030623; 20140038059; 20140038060; 20140045015; 20140045016; 20140045017; 20140045019; 20140045020; 20140045021; 20140045022; 20140045065; 20140050910; 20140050972; 20140057168; 20140057169; 20140057172; 20140057173; 20140057179; 20140065479; 20140072837; 20140072843; 20140072877; 20140087214; 20140087250; 20140087251; 20140087257; 20140093780; 20140093787; 20140099560; 20140106219; 20140107326; 20140113202; 20140113203; 20140117940; 20140125292; 20140127567; 20140127575; 20140132220; 20140134499; 20140134501; 20140134521; 20140138591; 20140141336; 20140141337; 20140141340; 20140147741; 20140147752; 20140154546; 20140154557; 20140154559; 20140154587; 20140154590; 20140162130; 20140162131; 20140166929; 20140166939; 20140170303; 20140170475; 20140170482; 20140170498; 20140170503; 20140170524; 20140173300; 20140176074; 20140176076; 20140178759; 20140178770; 20140178772; 20140184162; 20140184172; 20140193712; 20140197801; 20140197805; 20140199585; 20140199599; 20140199600; 20140205905; 20140212752; 20140212763; 20140212770; 20140220417; 20140220422; 20140227432; 20140230887; 20140234693; 20140234705; 20140234711; 20140234712; 20140234713; 20140234727; 20140234732; 20140242445; 20140242453; 20140242469; 20140242474; 20140248521; 20140248537; 20140264198; 20140266075; 20140272132; 20140272489; 20140272531; 20140272553; 20140272558; 20140272567; 20140272568; 20140272574; 20140272576; 20140272577; 20140272578; 20140272579; 20140272580; 20140272583; 20140272591; 20140287305; 20140287325; 20140287330; 20140295268; 20140295270; 20140295290; 20140302354; 20140302400; 20140308562; 20140308583; 20140308585; 20140308588; 20140310951; 20140312269; 20140314948; 20140315072; 20140315097; 20140322579; 20140322602; 20140329120; 20140329131; 20140329150; 20140335406; 20140335410; 20140335411; 20140342200; 20140342228; 20140342240; 20140346618; 20140349182; 20140349186; 20140356708; 20140356735; 20140363735; 20140363746; 20140370380; 20140370387; 20140376160; 20140377635; 20140377667; 20140377668; 20150002162; 20150004444; 20150004480; 20150004482; 20150004488; 20150004495; 20150010460; 20150010784; 20150017541; 20150017543; 20150024279; 20150030856; 20150030939; 20150037675; 20150037686; 20150037690; 20150044517; 20150044533; 20150044556; 20150044571; 20150044573; 20150050535; 20150050564; 20150050565; 20150056488; 20150056507; 20150056509; 20150056514; 20150056516; 20150062687; 20150064568; 20150064578; 20150064580; 20150069307; 20150072225; 20150072232; 20150072247; 20150079477; 20150079483; 20150079484; 20150086876; 20150086877; 20150089797; 20150093631; 20150093647; 20150093653; 20150099165; 20150099184; 20150099185; 20150099187; 20150099191; 20150099192; 20150102257; 20150104701; 20150104712; 20150104716; 20150111078; 20150111099; 20150118558; 20150118565; 20150118572; 20150125595; 20150125752; 20150125759; 20150125761; 20150137030; 20150140206; 20150140427; 20150140434; 20150140446; 20150147624; 20150147642; 20150147645; 20150147662; 20150152566; 20150155546; 20150155557; 20150162139; 20150162588; 20150162603; 20150171414; 20150171426; 20150179976; 20150180001; 20150180023; 20150180087; 20150180249; 20150188125; 20150188191; 20150191841; 20150194702; 20150200390; 20150200422; 20150207147; 20150207174; 20150207176; 20150210044; 20150214529; 20150214573; 20150214577; 20150221936; 20150221983; 20150221987; 20150228980; 20150236343; 20150236372; 20150236378; 20150236380; 20150243972; 20150243973; 20150243987; 20150243988; 20150244041; 20150249247; 20150249262; 20150263342; 20150263379; 20150263543; 20150270552; 20150270573; 20150280219; 20150280229; 20150280267; 20150288031; 20150295241; 20150295275; 20150295276; 20150303481; 20150311509; 20150311525; 20150311564; 20150318543; 20150318570; 20150318572; 20150318578; 20150318580; 20150325843; 20150325852; 20150325880; 20150325882; 20150325884; 20150333310; 20150333315; 20150333370; 20150340679; 20150340739; 20150349338; 20150357646; 20150364747; 20150364748; 20150364755; 20150364791; 20150364794; 20150364795; 20150364796; 20150372296; 20150372305; 20150372346; 20150372349; 20150373831; 20150377977; 20150380355; 20150380731; 20150380772; 20150380777; each of which is expressly incorporated herein by reference in its entirety.


SUMMARY OF THE INVENTION

The present technology includes the use of an all-inorganic electrolyte system suitable for a wide variety of energy storage systems, especially lithium ion chemistry. The key composition of the solvent system provides a combination of two distinct classes of phosphorus compounds; PA and Pz, in an electrolyte system which substantially excludes (e.g., <2% by weight) organic carbonates. Each class of phosphorus-based compounds has both benefits and limitations alone. Yet, each of the sets of limitations can be designed in such a fashion as to retain the beneficial properties of each distinct class, while simultaneously significantly reducing or altogether eliminating the limitations of either class alone. Preferably, a MP compound, e.g., a phosphate, phosphonate, phosphinate, phosphine or phosphine oxide, with substituents that are generally non-reactive with the battery chemistry and stable under battery operational conditions, is provided in the electrolyte system as well.


The inorganic solvent system can greatly improve lithium ion batteries by better controlling the issues of volatility, flammability, and thermal and electrochemical instability inherent to organic solvents that lead to significant cell degradation and catastrophic failure. Additionally, the PA/Pz solvent system has improved performance pertaining to the aforementioned issues as they relate to the bulk electrolyte solution and the SEI. The SEI formed in the PA/Pz system in a lithium ion battery is believed to be breakdown products of the PA and Pz (and also the MP, if present), i.e., rich in phosphorus-nitrogen compounds, which may be largely inorganic, even if the substituents of the PA, Pz, or MP include organic ligands. This SEI is believed to be distinct from the SEI formed using other electrolyte chemistries. Note that the SEI at the anode and cathode will differ, due to the relative preponderance of oxidative and reductive processes at each. Therefore, it is preferred that a stable SEI form from the electrolyte components at all electrochemically active regions of the battery, or other energy storage device. When the electrolyte is used in other types of devices, the formation and criticality of an SEI is dependent on the characteristics of the respective electrochemical system.


The SEI acts to prevent direct contact of the electrolyte molecules with the surface of the electrode, while allowing charge carrier transport. Because the surface of the electrodes is dynamic, a small portion of the SEI redevelops during each charge/discharge cycle from the electrolyte components in contact with the electrode interface with the bulk electrolyte. The cathode also has an SEI, though the cathode surface is less dynamic than the anode. Therefore, the electrolyte medium itself is involved in electrochemical reactions with the electrodes, and should be selected to provide stability under such conditions. It is noted that the difficult-to-characterize chemical makeup of the SEI formed from the PA and Pz is an efficient free radical quencher, and thus once formed, provides an effective barrier that protects the bulk electrolyte from continuous degradation.


See, Sazhin, Sergiy V., Mason K. Harrup, and Kevin L. Gering. “Characterization of low-flammability electrolytes for lithium-ion batteries.” Journal of Power Sources 196.7 (2011): 3433-3438; Harrup, Mason K., et al. “Unsaturated phosphazenes as co-solvents for lithium-ion battery electrolytes.” Journal of Power Sources 278 (2015): 794-801; Xu, Kang, et al. “An attempt to formulate nonflammable lithium ion electrolytes with alkyl phosphates and phosphazenes.” Journal of The Electrochemical Society 149.5 (2002): A622-A626; Gering, Kevin L., et al. Section IV. D. 3 for DOE 2013 Annual Report: Novel Phosphazene-Based Compounds to Enhance Safety and Stability of Cell Chemistries for High Voltage Applications (INL). No. INL/EXT-13-30529. Idaho National Laboratory (INL), 2013; Rollins, Harry W., et al. “Fluorinated phosphazene co-solvents for improved thermal and safety performance in lithium-ion battery electrolytes.” Journal of Power Sources 263 (2014): 66-74; Choi, Ji-Ae, Yongku Kang, and Dong-Won Kim. “Lithium polymer cell assembled by in situ chemical cross-linking of ionic liquid electrolyte with phosphazene-based cross-linking agent.” Electrochimica Acta 89 (2013): 359-364; Gering, Kevin, M. Harrup, and E. Dufek. “Integrated Carbon-Reduced Battery Chemistries for Safer Alternative Li-Ion Cells.” 224th ECS Meeting (Oct. 27-Nov. 1, 2013). Ecs, 2013; Harrup, Mason, Eric J. Dufek, and Kevin L. Gering. “Integrated Carbon-Reduced Battery Chemistries for Safer Alternative Li-Ion Cells.” Meeting Abstracts. No. 14. The Electrochemical Society, 2013; Bieker, Georg, Martin Winter, and Peter Bieker. “Electrochemical in situ investigations of SEI and dendrite formation on the lithium metal anode.” Physical Chemistry Chemical Physics 17.14 (2015): 8670-8679; Harrup, Mason K., et al. “Unsaturated phosphazenes as co-solvents for lithium-ion battery electrolytes.” Journal of Power Sources 278 (2015): 794-801; Wu, Bingbin, et al. “An electrochemically compatible and flame-retardant electrolyte additive for safe lithium ion batteries.” Journal of Power Sources 227 (2013): 106-110; Harrup, Mason K., et al. “Phosphazene Based Additives for Improvement of Safety and Battery Lifetimes in Lithium-Ion Batteries.” ECS Transactions 41.39 (2012): 13-25; Zhang, Qing, et al. “Improved thermal stability of LiCoO2 by cyclotriphosphazene additives in lithium-ion batteries.” Chemistry Letters 34.7 (2005): 1012-1013; Benson, Michael T., Mason K. Harrup, and Kevin L. Gering. “Lithium binding in fluorinated phosphazene trimers.” Computational and Theoretical Chemistry 1005 (2013): 25-34; Zhang, Sheng Shui. “A review on electrolyte additives for lithium-ion batteries.” Journal of Power Sources 162.2 (2006): 1379-1394; Cao, Xia, et al. “Novel phosphamide additive to improve thermal stability of solid electrolyte interphase on graphite anode in lithium-ion batteries.” ACS applied materials & interfaces 5.22 (2013): 11494-11497., each of which is expressly incorporated herein by reference in its entirety. See also U.S. Pat. Nos. 6,146,787; 6,544,690; 6,723,349; 7,008,564; 7,282,295; 7,282,296; 7,282,302; 7,285,362; 7,390,591; 7,491,458; 7,608,178; 7,645,543; 7,666,233; 7,691,289; 7,704,468; 7,781,108; 7,829,212; 7,838,144; 7,858,223; 7,864,397; 7,998,626; 8,048,571; 8,114,171; 8,182,943; 8,202,649; 8,293,398; 8,323,820; 8,334,075; 8,361,664; 8,389,147; 8,455,131; 8,459,213; 8,501,339; 8,529,867; 8,652,686; 8,652,692; 8,658,304; 8,671,684; 8,673,477; 8,709,679; 8,778,522; 8,828,573; 8,828,574; 8,828,575; 8,916,291; 8,932,771; 8,980,602; 8,986,638; 9,051,629; 9,061,261; 9,123,941; 9,136,568; 9,187,834; 9,187,835; 9,190,695; 9,200,375; 9,206,210; 9,257,720; 9,269,998; 9,287,573; 20040009404; 20050255385; 20080096056; 20100094042; 20120088162; 20130089793; 20130259776; 20140140912; 20140342240; 20150340739; each of which is expressly incorporated herein by reference in its entirety.


In one embodiment, the PA/Pz solvent mixture includes the addition of an inorganic MP compound to further improve (reduce) the viscosity and ionic conductivity (increase) of the solvent mixture without adversely impacting the mixture's volatility, flammability, and thermal stability. At operating temperatures of 0° C.−50° C., the MP is typically provided, whereas in case of high temperature operation, the viscosity of the PA and Pz may be sufficiently low to permit efficient operation without the MP. This addition makes the solvent an ideal electrolyte for high discharge rate battery applications. Further, due to the greatly increased electrochemical window of stability versus organic systems, the use of high energy electrode couples is provided. Numerous examples of these couples exist, but are not in current use due to the limitations of the traditionally used organic electrolyte systems.


There are well documented inherent limitations in current lithium ion battery technologies. Some of these limitations arise from the organic electrolyte solvents due to their volatility, flammability, and thermal and electrochemical instability as they pertain to bulk electrolyte solution and the SEI. According to the present technology, the organic electrolyte solvents may be replaced with an all-inorganic electrolyte solvent system. “All-inorganic” is not intended to exclude organic substituents on inorganic core molecules. For example, 95% or greater by weight of the solvent may comprise phosphorus-containing compounds, and preferably 98% or greater by weight. Small amounts of other components are acceptable, so long as they do not greatly increase the vapor pressure or flammability of the composite.


In a preferred embodiment, the electrolyte solvent system is composed solely of phosphorus-compounds as a mixture of primary solvent PA derivatives and co-solvent Pz derivatives with a suitable supporting salt, i.e., a supporting lithium salt, in the case of a lithium battery. In addition, an inorganic MP compound can be added to this mixture, for example to further improve the solvent's capacity to work for high discharge applications without impacting the other benefits of the PA/Pz mixtures. In battery usage, the solvent system should solvate the charge carrier ion, i.e., a metal ion, to permit charge carrier densities of at least 0.1M, more preferably 0.5M, and most preferably greater than 1.0M. Further, in battery usage, the solvated charge carrier ions should not be tightly complexed to the solvent, and therefore the effective charge carrier ion should be the metal ion itself and not a solvent-molecule bound metal ion. In some cases, a minor portion of the electrolyte may bind charge carriers, especially if a source of charge carriers is provided in excess with respect to the complex-forming component. Further, while the solvent system is preferably non-reactive with the static battery chemistry, is preferably has a sufficient level of reactivity with the electrodes during battery cycling to form an SEI to effectively isolate the bulk electrolyte from the electrode surface, while permitting ion mobility through the SEI to the electrodes. Useful characteristics of the electrolyte are lack of flammability in air at standard temperature and pressure, low vapor pressure at 30° C. (e.g., less than 50 mBar, preferably less than 10 mBar, more preferably less than 5 mBar, and most preferably less than 1 mBar, all at 25° C.), low viscosity at 30° C. (≤30 cp), low toxicity (or reasonable method for detoxification), and an efficient biodegradation pathway at the end of the useful life.


Other types of batteries than lithium may be provided, such as sodium, potassium, aluminum, magnesium, manganese, vanadium, and the like. In such cases, the supporting salt and appropriate electrodes will of course correspond to the battery chemistry. In some cases, the solvent is not an electrolyte, or is provided as a potential electrolyte solvent prior to addition of a charge carrier. The solvent finds particular application in energy storage devices.


As used herein, the term “energy storage device” means and includes a device configured and comprising materials formulated to convert stored chemical energy into electrical energy or electrical energy into chemical energy. The energy storage device may include, but is not limited to, a battery or a capacitor. By way of example only, the energy storage device may be a metal-ion battery, a metal battery (e.g., Li, Na, K, Mg, Mn, V, etc.), an ultracapacitor, or a supercapacitor. In the case of capacitive energy storage systems, the formation of an SEI is not critical.


The pendant groups on the PA compound may be selected based on desired properties of the PA compound, such as to achieve sufficient stability, viscosity, flammability, salt solubility, ion transport, and cell cyclability properties of the PA compound to be used as the electrolyte or in the electrolyte solution. A desired balance of these properties may be achieved by appropriately selecting the pendant groups. The PA compound may be tailored to exhibit a low viscosity at room temperature, stability with respect to the electrochemical system chemistry (e.g., toward lithium or other metal, e.g., a high lithium or sodium salt, or other alkali metal, alkaline earth metal, transitional metal, or post transition metal salt) solubility, stability at high voltage, low flammability, and low volatility by appropriately selecting the pendant groups. The viscosity of the PA compound may be directly proportional to the molecular weight of the PA compound, which is, in turn, affected by the molecular weight of the pendant groups. By minimizing the molecular weight of the pendant groups, the PA compound may exhibit a viscosity within the desired range. To achieve the desired viscosity, the pendant groups may be selected to produce an asymmetric PA compound, i.e., a PA compound having different substituents on the phosphorus atom, which is believed to minimize molecular scale ordering and discourage a high extent of solvent self-association, aggressive multi-dentate bridging with an ionic species, and the generation of ordered or crystalline structures. Note that the viscosity of the mixed-component solvent is not directly related to the viscosity of the respective components, but as a first approximation, a lower viscosity of a significant solution component will yield a lower viscosity aggregate solution. Note also that addition of the supporting salt to the aggregate solution may also alter the viscosity.


The phosphorus substituents may also be selected such that the PA compound does not easily conform to solvate cations past mono-dentate coordination, including electron withdrawing moieties, such as fluorine. The PA compound may also be formulated in the electrolyte solution with dissimilar compounds to avoid solvent-to-solvent molecular association. These properties may directly impact the charge transfer process in the energy storage device where ions need to be able to readily associate and de-associate with solvent members through ion solvation, which has thermodynamic and kinetic costs in terms of energy and time requirements. Thus, selecting the pendant groups to achieve lower viscosity of the PA compound may additionally make the energy storage device more efficient by economizing charge transfer at each electrode interface. If, however, the PA compound is to be used as an additive in the electrolyte solution, the viscosity may be greater than the range described below to account for mixture effects with the electrolyte solution. The pendant groups may also be selected to provide the PA compound with sufficient electrochemical stability for use in the electrochemical environment of the energy storage device.


The pendant groups may also be selected such that the PA compound has a supporting salt solubility of at least about 1.0 M concentration at room temperature. If, however, the PA compound is to be used as an additive in the electrolyte solution, the salt solubility may be less than the above-mentioned concentration to account for mixture effects with the electrolyte solution. The salt solubility of the PA compound may also be improved by interactions with other components of the electrolyte solution. However, the PA compound may still have the ability to desolvate from the supporting salt cations to enable adequate cycling efficiencies and allow acceptable rate capabilities.


The pendant groups on the PA compound may be selected such that the PA compound is a liquid at room temperature (from about 20° C. to about 25° C.) and at the temperature of use, e.g., 0° C. or below to 60° C. or above, is stable at a temperature greater than about 150° C., and is substantially non-flammable at operating temperatures to which the electrolyte solution is exposed, e.g., ≤65° C. The PA compound of the electrolyte solution may also be stable at high voltages, such as greater than about 4.5 V, during cycling of the energy storage device including the electrolyte solution. The pendant groups on the PA compound may be selected such that the PA compound has an increased flash point and a decreased flame duration as compared to organic electrolytes, resulting in reduced flammability of the electrolyte solution.


The melting point of the PA compound may be in a range of from about −30° C. to about 10° C. so that the PA compound is a liquid at room temperature and at the temperature of use. Note that the PA compound is a component of the electrolyte solution, and therefore the melting point of the PA compound alone is not dispositive. Since the PA compound is to be used in the energy storage device, such as a battery, the temperature of use may be within a range of from about −25° C. to about 150° C. To maintain the PA compound as a liquid, the pendant groups may include at least one of a fluorinated alkyl group, an aryl group, the organosilyl group, an oxygen-containing organic group, and a branched organic group on the nitrogen atom, and different R groups (R1, R2, R3) may be used on the phosphorus atom. By selecting the X group from these functional groups, crystal packing may be disrupted so that the PA compound may remain a liquid at room temperature.


A phosphine oxide functional group bonded to the nitrogen atom of the PA compound, i.e., X is [—P(═O)R2], may be avoided because the P═O bond is strongly attracted to lithium ions.


The term “alkyl” means and includes a saturated, unsaturated, straight, branched, or cyclic hydrocarbon containing from one carbon atom to ten carbon atoms. Examples include, but are not limited to, methyl, ethyl, propyl(n-propyl, isopropyl, cyclopropyl), butyl(n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl(n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, cyclopentyl), hexyl(isohexyl, cyclohexyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl), heptyl, octyl, nonyl, or decyl. The term “alkoxy” means and includes an alkyl group linked to an oxygen atom. The alkoxy group may include, but is not limited to, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, an octoxy group, a nonoxy group, or a decoxy group, or an alkoxy-substituted alkoxy group (i.e., a polyether group), such as a methoxy methoxy group, a methoxy ethoxy group, an ethoxy methoxy, an ethoxy ethoxy group, a methoxy ethoxy ethoxy group, etc. The term “aryl” means and includes a hydrocarbon with alternating single and double bonds between carbon atoms forming a ring. Examples include, but are not limited to, a phenyl group, a tolyl group, or a naphthyl group. The aryl group may also contain a heteroatom, such as sulfur (thiophene, benzothiophene, etc.), oxygen (furan, benzofuran, etc.), or nitrogen (pyrrole, indole, pyridine, pyrimidine, imidazole, pyrazole, etc.). The term “aryloxy” means and includes an aryl group linked to an oxygen atom. In addition to the oxygen-containing groups (i.e., alkoxy, aryloxy) mentioned above, functional groups including other heteroatoms, such as sulfur or nitrogen, may be present in the pendant group. The heteroatom may link, for example, the alkyl group or the aryl group to the phosphorus atom of the PA compound. By way of example only, the sulfur or nitrogen analogue may include, but is not limited to, an alkylsulfide, an alkylamine, an arylsulfide, or an arylamine. The term “organosilyl” means and includes a compound having at least one carbon-silicon bond. At least one of an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or a halogen group may be bonded to the silicon atom. The groups bonded to the silicon atom may be the same as, or different from, one another. The alkyl group may be further substituted, such as with a halogen. The aryl group may be further substituted, such as with a halogen, an alkyl group, or a haloalkyl group. By way of example only, the organosilyl may be a trialkylsilyl group. The term “halo” or “halogen” means and includes fluoro, chloro, bromo, or iodo. Any of the above-mentioned functional groups may be further substituted with at least one substituent, such as with a halogen, a carboxyl, a carbonyl, a C(O)(alkyl), a carbonate, another keto functional group, an amine, an alkyl, an alkoxy, an alkylthio, an amide, an alkylamino, a dialkylamino, a haloalkyl, a hydroxyalkyl, an alkoxyalkyl, a cyano, a sulfonyl group, or a phosphate group. The cationic pendant group may include, but is not limited to, an ionic form of an aromatic amine, an aryl amine, or an aliphatic amine, such as a nitrogen-containing aryl group, a primary amine, a secondary amine, or a tertiary amine. The aromatic amine may be an aniline group. The nitrogen-containing aryl group may include, but is not limited to, a pyrrole group, an imidazole, a pyrazole, a pyridine group, a pyrazine group, a pyrimidine group, or a pyridazine group. By way of example, the amine group may be a methyl amino group or a dimethyl amino group.


The viscosity of the PA compound alone, or the solvent solution as a whole, may be within a range of from about 1 centipoise (cP) (about 0.001 Pas) to about 30 cP (about 0.03 Pas) at 20° C. or 30° C. or 35° C., such as from about 1 cP (about 0.001 Pas) to less than or equal to about 10 cP (about 0.01 Pas) at 20° C. or 30° C. or 35° C. or from about 1 cP (about 0.001 Pas) to less than or equal to about 7 cP (about 0.007 Pas) at 20° C. or 30° C. or 35° C.


The MP compound, if provided may be a simple organophosphates, organophosphonates, organophosphinates, and/or organic phosphine oxide alkyl and/or aryl derivative. Organophosphates are fully esterified derivatives of phosphoric acid and are conveniently synthesized employing light aliphatic or aryl alcohols. Organophosphates are widely employed both in natural and synthetic applications because of the ease with which organic groups can be linked together. Organic phosphine oxides are similar in structure to the organophosphates, except they contain direct phosphorus-carbon linkages, instead of being bound through a heteroatom, like oxygen. Organophosphonates and organophosphinates have both ester and phosphorus-carbon linkages. These compounds are also readily synthesized, for example as a by-product of the Wittig reaction. Another common route to phosphine oxides is the thermolysis of phosphonium hydroxides. As in the case with the organophosphates, the R-groups may be any light aliphatic or aryl group, and most preferred is for each molecule to have a plurality of differing groups attached to the same central phosphorus.


The metal salt may be a salt of lithium, sodium, potassium, magnesium, manganese, or other alkali metal or alkaline earth metal, or vanadium, or other metals. The solvent solution as a whole, may have a high salt solubility, such as from about 0.1 to 5 M, and for example, may be 0.5 M to about 1.2 M, or 0.8 to 1.1 M, in a solution of a metal salt, such as in a lithium salt solution, a sodium salt solution, other alkali metal solution, alkaline earth metal solution, transitional metal solution, or post transition metal solution. By way of example only, the lithium salt may be lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium perchlorate (LiClO4), or combinations thereof. The solvent solution with a 1.0 M supporting salt at room temperature may have a conductivity of at least about 5 mS/cm.


The solvent system may provide a good ion cyclability in the energy storage device, such as at least a C/l equivalent cycling rate. However, when used in consumer electronics, the battery including the solvent may exhibit a lower cycling rate.


The various compounds according to the present technology are produced according to standard techniques, and may be available as commodity products.


The electrolyte solution including the PA compound may be used in an energy storage device (e.g., a battery or capacitor) that includes a positive electrode (e.g., a cathode), a negative electrode (e.g., an anode) separated from the positive electrode, and an optional separator between the electrodes, with an SEI layer forming at a surface of the electrodes. The electrolyte solution is in contact with the positive electrode and the negative electrode, but may be positioned in the separator. By way of example, the energy storage device may be a lithium battery containing the electrolyte solution.


It is therefore an object to provide an electrolyte solvent formulation comprising: a phosphoranimine; a phosphazene; and optionally a monomeric phosphorus compound. The formulation preferably has a melting point below 0° C. The formulation preferably has a vapor pressure of combustible components at 60.6° C. sufficiently low to not produce a combustible mixture in air, e.g., a vapor pressure of less than 40 mmHg at 30° C. The phosphoranimine, phosphazene, and monomeric phosphorus compounds preferably has no direct halogen-phosphorus bonds.


It is a still further object to provide an electrolyte solvent formulation comprising: a phosphoranimine; and a phosphazene; having a melting point below 0° C., and a vapor pressure of combustible components at 60.6° C. sufficiently low to not produce a combustible mixture in air, wherein none of the phosphoranimine and phosphazene compounds has any direct halogen-phosphorus bonds.


The formulation preferably comprises a supporting salt having a concentration of at least 0.1M charge carrier ions. The supporting salt, may comprise a supporting lithium salt effective to render the electrolyte solvent formulation suitable for use as an electrolyte in a lithium ion battery, e.g., LiPF6.


The monomeric phosphorus compound may comprise a phosphate, phosphonate, phosphinate, or phosphine. The MP preferably has at least two different types of pendent groups. The monomeric phosphorus compound may comprise an organophosphate compound in an amount sufficient to achieve a viscosity of the formulation of less than about 30 cp at 35° C.


The monomeric phosphorus compound may be present in an amount of between 10% and 50% by volume.


The phosphoranimine typically has the structure: X—N═P(R1, R2, R3), wherein X, R1, R2, and R3 are independently selected from the group consisting of inorganic and organic functional groups, wherein R1, R2, and R3 are represented by at least two different substituents. X may be selected from the group consisting of an organosilyl group and a tert-butyl group. R1, R2, and R3 may be independently selected from the group consisting of an alkoxy group, and an aryloxy group.


The phosphazene may comprise a plurality of phosphazenes having respectively different pendent group substitution. The phosphazene may comprise a substituted phosphazene having substituents selected from the group consisting of alkoxy and fluorinated alkoxy groups. The substituted phosphazene may comprise at least one of an ethoxy substituent and a 2,2,2-trifluoroethoxy substituent. The phosphazene may be present in an amount of between 0.1% and 50% by volume, and preferably in an amount of between 10% and 20% by volume.


The formulation preferably comprises less than about 2% by weight of organic compounds consisting essentially of at least one of carbon, hydrogen, and oxygen.


The phosphoranimine is preferably present in an amount of between 20-50% by volume, the phosphazene is preferably present in an amount of between 3-15% by volume, and the monomeric phosphorus compound is preferably present in an amount of 20-50% by volume.


The formulation may be provided with a battery or other energy storage device, having an anode, a cathode, a separator, and a supporting salt.


In a battery, a solid electrode interphase layer consisting essentially of breakdown products of at least one of the phosphoranimine, the phosphazene, and the monomeric phosphorus compound forms near the electrodes.


It is another object to provide an electrolyte for use in a lithium battery, which is liquid at 0° C., comprising a supporting lithium salt, and a solvent comprising less than about 2% purely organic compounds consisting essentially of carbon, hydrogen and oxygen. The electrolyte preferably has a vapor pressure of less than 40 mmHg at 30° C. The electrolyte may be provided in combination with: an anode, a cathode, and a separator configured to separate the anode and the cathode and permit lithium ion permeability there-through. A solid electrolyte interphase layer selectively forms near a surface of the anode and cathode from degradation products of the electrolyte. The formed solid electrolyte interphase layer is preferably stable for at least 245 days at 60° C. The electrolyte preferably comprises a phosphoranimine, a phosphazene, optionally a monomeric phosphorus compound, and the supporting lithium salt. The solid electrolyte interface layer formed by the electrolyte with the electrodes is more preferably thermally stable ≥80° C. At least one of the phosphoranimine and the phosphazene may comprise a plurality of different phosphoranimines or different phosphazenes having a plurality of respectfully different substituents.


The electrolyte preferably comprises between 0.1% and 50% of the phosphazene by volume and between 10% and 20% of the phosphazene by volume. The electrolyte optionally comprises the up to 50% by volume of the monomeric phosphorus compound.


A further object provides a rechargeable lithium ion battery, comprising an anode, a cathode, a separator, an electrolyte, a supporting lithium salt, and a solid electrolyte interphase layer, the electrolyte comprising at least one phosphoranimine, at least one cyclic phosphazene, and at least one organophosphate, wherein the electrolyte has a viscosity of ≤30 cp at 35° C., a concentration of lithium ions of at least 0.2M, and a vapor pressure of ≤40 mmHg at 30° C., wherein the solid electrolyte interphase layer is formed by degradation of the electrolyte in proximity to the cathode and the anode and is stable against degradation at 65° C.


It is further object to provide a lithium ion battery having an operating temperature range which extends beyond 0° C. to 50° C., and has an electrolyte viscosity of less than 30 cp within the operating temperature range.


It is another object to provide a method of forming a battery, comprising: providing an anode, a cathode, a separator, and a electrolyte solvent formulation comprising: a phosphoranimine, a phosphazene; and a supporting salt, the solvent formulation having a melting point below 0° C., and a vapor pressure of combustible components at 60.6° C. sufficiently low to not produce a combustible mixture in air, wherein none of the phosphoranimine, and phosphazene has any direct halogen-phosphorus bonds; and cycling the battery at to form a solid electrolyte interface formed from products of the phosphoranimine and phosphazene. The electrolyte solvent may further comprise a monomeric phosphorus compound, e.g., a, organophosphate. The electrolyte solvent formulation preferably has a viscosity of less than about 30 cp at 35° C.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is the basic chemical structure of the primary phosphoranimine from which other derivatives may be derived by replacement of X, R1, R2, and R3 with various function groups as described within the claims herein.



FIG. 2 is the example chemical structure of the co-solvent phosphazene, in this example, an embodiment using ethoxy and 2,2,2-trifluoroethoxy functional groups.



FIG. 3 shows the benefits of low levels of FM2 (˜10%) on battery performance.



FIG. 4 shows that the presence of FM2 in SEI layer is beneficial to the battery.





DETAILED DESCRIPTION OF THE INVENTION

The PA and Pz compounds are considered inorganic compounds due to their phosphorus-nitrogen (P═N) parent structure. The MP component is considered inorganic due to the core P atom in the parent structure as the primary atom that substituent atoms or molecules are bonded as defined by IUPAC.


The technology involves the preparation of a totally inorganic electrolyte which may have application in lithium ion batteries. It employs an admixture of a lower molecular weight phosphorus-based compounds, from the class of molecules known as the PAs as the principal solvent and a higher molecular weight phosphorus-based compound, from the class of molecules known as the Pzs as a co-solvent, as well as a suitable supporting salt (such as LiPF6, etc.) to formulate the novel electrolyte. This particular combination of substances obviates the well-known safety and longevity problems associated with current organic-based technologies, while offering numerous other benefits to battery reliability and performance. An MP compound may be provided which, e.g., serves as a viscosity reducer for the solution.


Compared to other organophosphorous compounds and other additives, Pzs showed the least degradation in battery performance. A key performance consideration is ionic conductivity of the solvent. The rate of ion transfer is influenced by the ionic conductivity of the electrolyte solvent. The conductivity itself is generally inversely proportional to the viscosity of the solvent—a less viscous fluid will transfer lithium ions more readily. Carbonates and other organic electrolyte solvents are generally well known to be good ionic conductors due to their low viscosity. However, they break down easily at elevated temperatures, as low as 50° C., which can easily be experienced during normal battery operation. This creates residue within the electrolyte that reduces the ionic conductivity, increases the viscosity, and potentially leads to runaway thermal events. The PA/Pz solvent mixture in this invention is designed to be a suitable carrier of lithium ions while improving the battery's safety and longevity.


PA possess the requisite high lithium salt solubility and low viscosity while Pz offer benefits to the electrochemical performance and formulation stability required to realize the next generation of lithium ion batteries. Taken together, this new electrolyte formulation allows for a totally inorganic electrolyte system, superior to current technologies. The Pz co-solvent maintains the high lithium salt solubility and introduces the beneficial properties of significantly improved electrochemical and thermal stability, leading to increased performance. The Pz component has been shown to increase the width of the electrochemical window—the range of voltages where there are no redox reactions occurring in the electrolyte—improving the durability of the battery over a larger range of voltages. As described in Rollins, H. W., Harrup, M. K., Dufek, E. J., Jamison, D. K., Sazhin, S. V., Gering, K. L., & Daubaras, D. L., “Fluorinated Phosphazene Co-solvents for Improved Thermal and Safety Performance in Lithium-ion Battery Electrolytes”, Journal of Power Sources, 263, 66-74 (2014), expressly incorporated herein by reference in its entirety, electrolyte solutions of 20% Pz with carbonates extends the electrochemical window up to 1.85V over the baseline 0.85 V window exhibited by carbonate solutions alone. This beneficial trend is should continue for PA/Pz mixtures and PA/Pz/MP mixtures. See also E. J. Dufek, M. L. Stone, D. K. Jamison, F. F. Stewart, K. L. Gering, L. M. Petkovic, A. D. Wilson, M. K. Harrup, H. W. Rollins, “Hybrid Phosphazene Anodes for Energy Storage Applications”, J. of Power Sources, 267 (2014) 347-355; and E. J. Dufek, J. R. Klaehn, H. W. Rollins, M. K. Harrup, D. Jamison, “Phosphoranimine-based Battery Electrolytes”, J. of Power Sources, pending (2014), each of which is expressly incorporated herein by reference in its entirety.


Both PA and Pz, as well as MP, have very low thermal degradation rates compared to pure carbonate electrolytes. Pz alone can act as a “free-radical sponge” when used in carbonate electrolytes to slow their thermal degradation. In Rollins et al (2015) supra, solutions containing only organic carbonate electrolytes completely degrade after about 55 days of being held at 60° C., leaving a black solid residue. Solutions containing both organic carbonate and quantities of Pz retained much of the carbonate through 245 days held at the same temperature, and only showed slight discoloration. Pz as a co-solvent with PA would be expected to further diminish the effects of degradation of the solvent in this invention.


Both solvents have lower vapor pressures than that of typical organic solvents including but not limited to ethylene carbonate, ethyl methyl carbonate, and diethyl carbonate. PA and Pz are well-known for their flame retardant properties and possess high thermal stability. These features provide lower volatility, lower flammability and greater thermal stability than current organic lithium ion battery solvents.


An MP compound, for example a simple alkyl or aryl derivative of phosphate ((R′O)—(R″O)— (R′″O)—P═O) or phosphine oxide (R′R″R′″P═O), or organophosphonate ((R′O)— (R″O)—(R′″)—P═O) or ((R′O)— (R″)— (R′″)—P═O) is provided. The R groups R′, R″, R′″ may be the same or different, for example an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, or a sulfur or nitrogen analogue thereof. These groups may be substituted with halogens, but the MP compound, like the PA and Pz, should lack direct phosphorus-halogen bonds, and all should lack hydroxyl groups. The substituents preferably are different, to reduce packing and suppress the melting point of the MP compound and the electrolyte as a whole. For example, the MP compound may be methanoyl, ethanoyl, isopropanoyl phosphate.


The all-inorganic PA/Pz solvent mixture (optionally including MP) will also improve the stability of the SEI layer. The SEI layer forms during battery charging as a result of the irreversible decomposition of the electrolyte at the surface of the electrode, creating a thin solid layer on the electrode. Once formed, the SEI layer isolates the electrode surface from the bulk solvent as the SEI layer does not readily allow diffusion of free solvent to the electrode surface, preventing further decomposition, and possesses low electrical conductivity. The SEI still allows for ease of lithium ion intercalation to the surface of the electrode to allow for continued battery operation.


The SEI layer will primarily be generated over the first few charging cycles averaging between 100 nm and 1 micron once fully formed. In typical carbonate solvents, the layer will grow slowly through additional cycles through further solvent decomposition that competes with the lithium intercalation, contributing to capacity fade over large number of cycles. The SEI stability is temperature-sensitive, and as the battery heats up as through normal use, the SEI will break down into the electrolyte and re-expose the electrode. The electrode will then readily react with fresh solvent to reform this layer, consuming more of the lithium ions and furthering the capacity fade. The SEI decomposition reaction is also exothermic and can lead to thermal runaway if not controlled. The SEI layers formed from carbonate-based solvents will break down at a relatively low temperature, as low as 55° C., which can easily be realized in typical lithium batteries.


The use of an electrolyte solvent mixture of primary PA solvent and the Pz co-solvent, and optionally MP, improves the stability of the SEI layer. Both PA and Pz have been separately evaluated with organic carbonate-based solvents. Battery cells using PA or Pz mixed with organic carbonate solvents show lower capacity fade compared to organic carbonate-only solvents, indicating that the SEI layer where PA or Pz is present is much more stable than in organic carbonate-only solutions. The solvent mixture will improve stability of the SEI layer as compared to an SEI layer in a carbonate-based battery and be much more stable under high charge/discharge rates.


Another benefit that the PA/PZ solvent mixture (optionally with MP) has in regards to the SEI layer is in improving the ionic conductivity of the SEI layer due to Pz. Battery cells using organic carbonate solutions have been evaluated via impedance spectroscopy with and without the addition of Pz. The impedance of the SEI layer is reduced when Pz is present in the electrolyte solvent, as well as retaining the higher stability described above. This would make it easier to transfer charge through the layer, allowing for faster discharge rates.


The syntheses of the individual constituents are herein described in detail as a means of non-limiting example.


MP Compound Synthetic Pathway


The MP compounds are preferably simple alkyl and/or aryl derivatives of organophosphates and/or organic phosphine oxides and/or organic phosphonates. Organophosphates are widely employed both in natural and synthetic applications because of the ease with which organic groups can be linked together. Organophosphates are conveniently synthesized employing light aliphatic or aryl alcohols according to the general reaction scheme given below:

OP(OH)3+ROH→OP(OH)2(OR)+H2O
OP(OH)2(OR)+R′OH→OP(OH)(OR)(OR′)+H2O
OP(OH)(OR)(OR′)+R″OH→OP(OR)(OR′)(OR″)+H2O


Organophosphinates and phosphonates are phosphate derivatives having one or two phosphorus-carbon bonds, respectively, with the remaining phosphorus bonds being oxygen/ester bonds. They may be prepared, for example, using an Arbuzov sequence or Michaelis-Arbuzov rearrangement, Abramov reaction, Pudovik reaction, Michaelis-Becker reaction, etc., from a corresponding phosphate. See Richardson, Rebekah Marie, New Synthesis and Reactions of Phosphonates, Doctoral Dissertation, U. of Iowa (2012), expressly incorporated herein by reference in its entirety.


Organic phosphine oxides are similar in structure to the organophosphates, except they contain only direct phosphorus-carbon linkages, instead of being bound through a heteroatom, like oxygen. These compounds are also readily synthesized through the two general reaction schemes shown below:


Phosphine oxides are frequently generated as a by-product of the Wittig reaction:

R3PCR′2+R″2CO→R3PO+R′2C═CR″2


Another common route to phosphine oxides is the thermolysis of phosphonium hydroxides. In the laboratory, phosphine oxides are usually generated by the oxidation, often accidentally, of tertiary phosphines: R3P+½ O2→R3PO


As in the case with the organophosphates, the R-groups may be any light aliphatic or aryl group, and most preferred is for each molecule to have a plurality of differing groups attached to the same central phosphorus.


PA Synthetic Pathway


The synthesis of PAs for this purpose was accomplished using the established Neilson and Wisian-Neilson methods. The synthetic route includes the preparation an initial aminophosphine which is then oxidized to the corresponding PA using elemental bromine. Maximization of LiPF6 solubility was accomplished by substituting the subsequent bromine group(s) on the PV center with various alkyl and etheric oxygen-containing pendant groups.


Pz Synthetic Pathway:


In an oven dried 500 ml flask, 50 g (0.144 moles) of the hexachlorocyclotriphosphazene trimer was dissolved in ˜300 ml anhydrous dioxane which was then added to the a solution of sodium ethoxide (under nitrogen at room temperature) and heated at sub-reflux for 5 hours and the reaction progress was monitored by 31P NMR. This solution was then cooled to room temperature and then added to a solution of sodium trifluoroethoxide (at RT under nitrogen). This solution was heated to sub reflux for ˜5 hours. This reaction was also followed by 31P NMR. When the reaction was complete, the solution was allowed to cool to room temperature and the excess ethoxides were quenched with water. The solution was neutralized with 2 M HCl. The solvent was removed by rotary evaporation leaving the Pz product (a liquid) and undissolved solid sodium chloride. The product separated from the salt by decantation and taken up in dichloromethane and washed with nanopure (18 MΩ cm) water in a separatory funnel six times to remove trace impurities. The dichloromethane was removed from the product on a rotary evaporator and the product was then dried in an argon purged vacuum oven for several days, refreshing the atmosphere with fresh UHP argon daily.


Although both classes of phosphorus compounds have been previously investigated individually, this work has been founded on the use of these compounds individually in combination with traditional organic carbonate-based solvents in an attempt to reduce the shortcomings of use of these solvents. According to the present technology, organic carbonates are generally excluded as a substantial component of the formulation altogether, to form a new all-inorganic electrolyte. For example, <2% of the solvent is organic carbonates. This electrolyte is compatible with most known lithium ion battery components in widespread use today. These include the anode, the cathode, electrode binders, and the mechanical separator, as well as common casing components. As such, the overall processes and key materials for the commercial manufacture of lithium ion batteries are unaltered from current methodologies. The embodiment of this invention is a lithium-ion based battery system that uses an electrolyte mixture of one or more PA components as the primary solvent, and one or more Pz components as the co-solvent. In the preferred embodiment, the mixture is composed primarily of one or more PA components (that is, Pz components comprising less than 50% of the solvent by volume). In a more preferred embodiment, the Pz components are present in the range of 10 to 20% by volume.


US Patent Application No. 20150340739 describes an embodiment of the PA. In the preferred embodiment, the PA includes at least one PA compound which has the chemical structure as shown in FIG. 1, where X is an organosilyl group or a tert-butyl group and each of R1, R2, and R3 is independently selected from the group consisting of an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. In another embodiment, each of R1, R2, and R3 is independently selected from a cationic pendant group, which includes but is not limited to an ionic form of an aromatic amine, an aryl amine, or an aliphatic amine, such as a nitrogen containing aryl group, a primary amine, a secondary amine, or a tertiary amine. The aromatic amine may be an aniline group. The nitrogen containing aryl group may include, but is not limited to, a pyrrole group, an imidazole, a pyrazole, a pyridine group, a pyrazine group, a pyrimidine group, or a pyridazine group. The PA compound, or mixture thereof, is designed to meet desired properties for lithium ion batteries, including low viscosity, high ionic conductivity, low vapor pressure, and non-flammability


In the embodiment, the Pz mixture includes at least one cyclic Pz compound, having a 6-membered alternating P—N ring structure, and with each phosphorus atom having 2 constituent functional groups attached to it. An example is shown in FIG. 2. In a more preferred embodiment, these functional groups include a combination of alkoxy and fluorinated alkoxy groups, as described in Rollins, Harry W., Mason K. Harrup, Eric J. Dufek, David K. Jamison, Sergiy V. Sazhin, Kevin L. Gering, and Dayna L. Daubaras. “Fluorinated phosphazene co-solvents for improved thermal and safety performance in lithium-ion battery electrolytes.” Journal of Power Sources 263 (2014): 66-74, expressly incorporated herein by reference in its entirety. One example of this preferred embodiment, is where these groups are, respectively, ethoxy (CH3—CH2—O—) and 2,2,2-trifluoroethoxy (CF3—CH2—O—).


In some embodiments, inorganic MP compounds are added for the purpose of further lowering the viscosity of the PA/Pz electrolyte mixture, while enhancing ionic conductivity. This is done to address some energy storage applications that demand a very fast charge/discharge rate (typically >3 C). The purpose for the selection of these inorganic-based compounds is three-fold. First, it maintains the all-inorganic nature of the electrolyte blend as previously asserted in this application. Second, one of the areas where PA and Pz compounds decompose into MP species is during the formation of the SEI layer during battery operation. As such, addition of these compounds will not adversely affect the SEI composition over a pure PA/Pz formulation, while retaining all of the desired beneficial electrical and physical properties inherent in the PA/Pz mixture. Third, these compounds are known to have a lower viscosity than either PA or Pz alone, achieving a total lower viscosity for the electrolyte formulation. In a preferred embodiment, the MP compounds will be present up to 20% by volume in the PA/Pz mixture.


EXAMPLE

A model of a lithium-ion battery using the mixture of PA and Pz were developed based on existing data on the characterization and testing of PA and Pz components, specifically referred to as PA2 and FM2, respectively. Parameters for the model using an equivalent circuit model were determined from data regression of impedance testing of FM2 in electrolyte mixtures, and from physical property values for viscosity and conductivity for PA2 and FM2 determined through experiment. The model used physical property relationships to project the performance of a battery that used only a mixture of PA2 and FM2. This model estimates the hydrodynamic and electrochemical properties of the PA2/FM2 electrolyte solvent and the battery performance using established property correlations for chemical mixtures. These relationships are based on standard trends for normal molecular interactions between compounds. Non-normal behavior can be exhibited in certain circumstances, but does not negate the novelty of this invention. The SEI was modeled from the results of the FM2 experimental data and is shown below for a range of compositions (from 0% to 100% FM2) to gauge the estimated range of performance.


The model was used to calculate the performance of a lithium-ion battery using various mixtures of PA2/FM2 (from 100% to 50% PA) at discharge rates from 1/10 C to 10 C. The following table is the voltage of a single battery cell at various state-of-charge (SOC) levels as a function of the battery electrolyte composition, the anticipated SEI layer composition, and the discharge rate.









TABLE 1







Estimated Battery Voltage during Discharge for Various PA2/FM2 Configurations









Discharge Rate













FM2
1/10 C Discharge
1 C Discharge
3 C Discharge
10 C Discharge









Solvent
in SEI
SOC




















Comp.
Layer
90%
60%
20%
90%
60%
20%
90%
60%
20%
90%
60%
20%























 0%
0%
4.0470
3.8459
3.7030
3.7046
3.5027
3.3600
2.9419
2.7400
2.5970
0.0273
0.0707
0.0700


FM2


10%
0%
4.0525
3.8506
3.7080
3.7512
3.5500
3.4079
3.0841
2.8822
2.7392
0.7465
0.5445
0.4015


FM2
50% 
4.0583
3.8564
3.7134
3.8096
3.6077
3.4647
3.2570
3.0551
2.9191
1.3230
1.1210
0.9780



100% 
4.0602
3.8582
3.7146
3.8281
3.6262
3.4832
3.3126
3.1106
2.9676
1.5080
1.3060
1.1630


25%
0%
4.0575
3.8555
3.7119
3.8011
3.5992
3.4562
3.2315
3.0296
2.8866
1.2378
1.3059
0.8929


FM2
50% 
4.0632
3.8613
3.7183
3.8588
3.6568
3.5138
3.4045
3.2025
3.0595
1.8143
1.6123
1.4693



100% 
4.0651
3.8631
3.7202
3.8773
3.6753
3.5324
3.4600
3.2580
3.1150
1.9993
1.7974
1.6544


35%
0%
4.0603
3.8584
3.7154
3.8294
3.6275
3.4845
3.3164
3.1145
2.9715
1.5029
1.3190
1.1760


FM2
50% 
4.0660
3.8641
3.7211
3.8871
3.6851
3.5422
3.4894
3.2874
3.1444
2.0974
1.8954
1.7524



100% 
4.0679
3.8660
3.7230
3.9056
3.7037
3.5607
3.5441
3.3429
3.1999
2.2824
2.0805
1.9375


50%
0%
4.0638
3.8619
3.7189
3.8650
3.6622
3.5200
3.4230
3.2211
3.0785
1.8762
1.6743
1.5313


FM2
50% 
4.0696
3.8677
3.7247
3.9226
3.7207
3.5777
3.5960
3.3940
3.2510
2.4527
2.2507
2.1077



100% 
4.0715
3.8695
3.7270
3.9411
3.7392
3.5966
3.6515
3.4495
3.3065
2.6377
2.4358
2.2928









Actual data shows that the base PA2 solvent will have a sufficiently low viscosity and corresponding high ionic conductivity to make it a suitable electrolyte in lithium battery applications at low discharge rates, when salted to a relevant level with a typical lithium salt, such as LiPF6. Using this data, the model shows that pure PA2 viscosity may not be sufficient as a pure solvent for high discharge rates (greater than 3 C). Addition of FM2 will increase the electrolyte thermal and electrochemical stability and can reduce the impedance of the solvent, improving the battery's performance. From this model, the benefit is apparent with low levels of FM2 (˜10%) and suggests diminishing returns at higher levels. FIG. 3 shows this influence. The model does not presently include the influence of MP compounds, which are expected to further depress the solution's viscosity without altering the other benefits of the PA2/FM2 (PA/Pz) mixture. The performance of batteries using the PA2/FM2/MP compounds would be expected to be better than what is shown in this model results for PA2/FM2 alone.


Similarly, the presence of FM2 in SEI layer is beneficial to the battery, as it appears the material offers lower resistance to ionic transfer to the electrodes, as shown in FIG. 4. Only a small amount of FM2 is required to achieve this, FM2 was added to carbonate solvents; additional FM2 beyond 50% within the SEI layer appears to have diminishing returns.


As used herein, the terms “comprising,” “including,” “containing,” “characterized by,” and grammatical equivalents thereof are inclusive or open-ended terms that do not exclude additional, unrecited elements or method steps, but also include the more restrictive terms “consisting of” and “consisting essentially of” and grammatical equivalents thereof. The scope of the disclosure is intended to encompass all combinations, subcombinations, and permutations of the various disclosures herein (regardless of whether in multiple-dependent format), and unless specifically limited by the claims, no particular aspect is considered essential. Likewise, the invention comprises materials and methods that facilitate production of an end product and portions of the end product. As used herein, the term “may” with respect to a material, structure, feature or method act indicates that such is contemplated for use in implementation of an embodiment of the disclosure and such term is used in preference to the more restrictive term “is” so as to avoid any implication that other, compatible materials, structures, features and methods usable in combination therewith should or must be, excluded.

Claims
  • 1. An electrolyte for use in a lithium battery, comprising: lithium ions in an amount of at least 0.1 M;at least one cyclic phosphazene;at least one phosphoranimine; andat least one monomeric phosphorus compound;wherein the electrolyte:is a liquid at ≤0° C.;has a viscosity of ≤30 cp at 35° C.; andhas a concentration volatile flammable components formed in an air headspace at 30° C. which is non-flammable.
  • 2. The electrolyte according to claim 1, wherein the at least one cyclic phosphazene is present in an amount of at least 3% and up to 50% by volume.
  • 3. The electrolyte according to claim 2, wherein the at least one phosphoranimine is present in an amount of at least 20% and up to 50% by volume.
  • 4. The electrolyte according to claim 3, wherein the at least one monomeric phosphorus compound is present in an amount of at least 10% and up to 50% by volume.
  • 5. The electrolyte according to claim 1, wherein has a vapor pressure of less than 40 mmHg at 30° C., a melting point above −30 C, and a viscosity ≥1 cp.
  • 6. The electrolyte according to claim 1, wherein the electrolyte consists essentially of compositions lacking direct phosphorus-halogen bonds.
  • 7. The electrolyte according to claim 1, in combination with: an anode,a cathode, anda lithium-ion permeable separator configured to separate the anode and the cathode.
  • 8. The electrolyte according to claim 7, further comprising an electrochemically-formed a solid electrolyte interface layer which stable against degradation at 65° C.
  • 9. The electrolyte according to claim 1, comprising between 0.1% and 50% by volume of the at least one cyclic phosphazene, between 10% and 50% by volume of the at least one phosphoranimine, and between 10% and 50% by volume of the at least one monophosphorus compound.
  • 10. An electrolyte for use in a lithium battery, which is liquid at 0° C., comprising: a supporting lithium salt;and a solvent comprising:cyclic phosphazenes in an amount of at least 0.1% and less than 70% by volume;phosphoranimines in an amount of at least 20% and less than 89.9% by volume; andmonomeric phosphorus compounds in an amount of at least 10% and less that 79.1% by volume;having a vapor pressure of less than 40 mmHg at 30° C.
  • 11. The electrolyte of claim 10, wherein the cyclic phosphazenes, phosphoranimines, and monomeric phosphorus compounds each lacks direct phosphorus-halogen bonds.
  • 12. The electrolyte according to claim 10, in combination with: an anode,a cathode, anda separator configured to separate the anode and the cathode and permit lithium ion permeability there-through,wherein the supporting lithium salt provides a lithium ion concentration of at least 0.2 M, and a solid electrolyte interphase layer selectively forms near a surface of the anode and cathode from degradation products of the electrolyte.
  • 13. The electrolyte of claim 12, wherein a solid electrolyte interface layer formed by the electrolyte with an electrode is thermally stable at ≥80° C.
  • 14. The electrolyte of claim 12, wherein the phosphoranimines comprise a plurality of different phosphoranimines, the different phosphoranimines respectively differing by at least having respectfully different substituents.
  • 15. The electrolyte of claim 12, wherein the electrolyte comprises between 3% and 50% of the cyclic phosphazenes by volume and between 20% and 50% of the phosphoranimines by volume.
  • 16. The electrolyte of claim 15, wherein the electrolyte comprises up to 50% by volume of the monomeric phosphorus compounds, and less than 2% purely organic compounds consisting essentially of carbon, hydrogen and oxygen.
  • 17. The electrolyte of claim 10, having a viscosity of ≥1 cp and ≤30 cp at 35° C., a melting point above −30 C, and a concentration of lithium ions of at least 0.2M.
  • 18. The electrolyte of claim 10, wherein the cyclic phosphazenes comprise a plurality of different cyclic phosphazenes having a plurality of respectfully different substituents.
  • 19. The electrolyte of claim 12, wherein the solid electrolyte interphase layer is stable against degradation at 65° C.
  • 20. The electrolyte of claim 12, wherein the solid electrolyte interphase layer is stable for at least 245 days at 60° C.
  • 21. An electrolyte formulation, comprising: a lithium salt in an amount sufficient to provide at least 0.1 M lithium ions;a phosphoranimine in an amount of at least 20% and less than or equal to 89.9% by volume;a cyclic phosphazene in an amount of at least 0.1% and less than or equal to 70% by volume; anda monomeric phosphorus compound in an amount of at least 10% and less than or equal to 79.9% by volume;the formulation having: a viscosity of ≤30 cp at 35° C., a melting point below 0° C., and a vapor pressure of ≤40 mmHg at 30° C., wherein none of the phosphoranimine, cyclic phosphazene, and monomeric phosphorus compound has any direct halogen-phosphorus bonds.
  • 22. The formulation of claim 21, wherein the supporting salt comprises LiPF6.
  • 23. The formulation of claim 21, wherein the monomeric phosphorus compound is selected from the group consisting of a phosphate, phosphonate, phosphinate, phosphine, and a phosphine oxide, having at least two different types of pendent groups.
  • 24. The formulation of claim 21, wherein the phosphoranimine has the structure:
  • 25. The formulation of claim 24, wherein X is selected from the group consisting of an organosilyl group and a tert-butyl group and R1, R2, and R3 are independently selected from the group consisting of a substituted or unsubstituted alkoxy group, and a substituted or unsubstituted aryloxy group.
  • 26. The formulation of claim 21, wherein the cyclic phosphazene comprises a plurality of cyclic phosphazenes having respectively different pendent group substitution, having substituents selected from the group consisting of alkoxy groups and fluorinated alkoxy groups.
  • 27. The formulation of claim 21, comprising less than 2% by weight of organic compounds consisting essentially of at least one of carbon, hydrogen, and oxygen.
  • 28. The formulation of claim 21, wherein the phosphoranimine is present in an amount of between 20-50% by volume, the cyclic phosphazene is present in an amount of between 3-15% by volume, and the monomeric phosphorus compound is present in an amount of 20-50% by volume, the formulation has a viscosity of at least 1 cp, and a melting point of at least −30 C.
  • 29. A battery comprising the formulation of claim 21, in combination with an anode, a cathode, and a separator.
CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a non-provisional of, and claims benefit of priority under 35 U.S.C. § 119(e) from, U.S. Provisional Patent Application No. 62/139,552, filed Mar. 27, 2015, the entirety of which is expressly incorporated herein by reference in its entirety.

US Referenced Citations (2140)
Number Name Date Kind
4126483 Donakowski et al. Nov 1978 A
4157941 Donakowski et al. Jun 1979 A
4159229 Donakowski et al. Jun 1979 A
4248868 Scartazzini et al. Feb 1981 A
4270957 Donakowski et al. Jun 1981 A
4483908 Zimmerman Nov 1984 A
4613676 Fuhrer et al. Sep 1986 A
4719288 Fuhrer et al. Jan 1988 A
4722877 Sammells Feb 1988 A
4727060 Buhlmayer et al. Feb 1988 A
4772433 Hesse Sep 1988 A
4810599 Kondo et al. Mar 1989 A
4828945 Nagata et al. May 1989 A
4863903 Fuhrer et al. Sep 1989 A
4931591 Buhlmayer et al. Jun 1990 A
4985317 Adachi et al. Jan 1991 A
5041346 Giles Aug 1991 A
5061581 Narang et al. Oct 1991 A
5071532 Taillet et al. Dec 1991 A
5110694 Nagasubramanian et al. May 1992 A
5114809 Nakacho et al. May 1992 A
5153080 Inubushi et al. Oct 1992 A
5153082 Ogino et al. Oct 1992 A
5176969 Miyabayashi et al. Jan 1993 A
5180645 More Jan 1993 A
5188783 Pierce Feb 1993 A
5190695 Sotomura Mar 1993 A
5229227 Webber Jul 1993 A
5337184 Helms et al. Aug 1994 A
5420000 Patel et al. May 1995 A
5426005 Eschbach Jun 1995 A
5443601 Doeff et al. Aug 1995 A
5455127 Olsen et al. Oct 1995 A
5474860 Abraham et al. Dec 1995 A
5523179 Chu Jun 1996 A
5532077 Chu Jul 1996 A
5548055 Narang et al. Aug 1996 A
5567783 Allcock et al. Oct 1996 A
5576120 Saidi Nov 1996 A
5580681 Fleischer Dec 1996 A
5582623 Chu Dec 1996 A
5591545 Miyashita et al. Jan 1997 A
5599435 Li et al. Feb 1997 A
5609972 Kaschmitter et al. Mar 1997 A
5633098 Narang et al. May 1997 A
5648011 Blonsky Jul 1997 A
5660948 Barker Aug 1997 A
5672446 Barker et al. Sep 1997 A
5672465 Patel et al. Sep 1997 A
5681357 Eschbach et al. Oct 1997 A
5686201 Chu Nov 1997 A
5688293 Oliver et al. Nov 1997 A
5698338 Barker et al. Dec 1997 A
5700298 Shi et al. Dec 1997 A
5707760 Stux et al. Jan 1998 A
5716421 Pendalwar et al. Feb 1998 A
5725968 Sato et al. Mar 1998 A
5728489 Gao et al. Mar 1998 A
5731104 Ventura et al. Mar 1998 A
5731105 Fleischer et al. Mar 1998 A
5733681 Li et al. Mar 1998 A
5741606 Mayer et al. Apr 1998 A
5744264 Barker Apr 1998 A
5753388 Koksbang et al. May 1998 A
5756231 Andrei et al. May 1998 A
5780182 Barker et al. Jul 1998 A
5783333 Mayer Jul 1998 A
5786110 Angell et al. Jul 1998 A
5789108 Chu Aug 1998 A
5789110 Saidi et al. Aug 1998 A
5795679 Kawakami et al. Aug 1998 A
5814420 Chu Sep 1998 A
5824434 Kawakami et al. Oct 1998 A
5830600 Narang et al. Nov 1998 A
5834135 Pendalwar et al. Nov 1998 A
5837015 Venugopal et al. Nov 1998 A
5843592 Barker et al. Dec 1998 A
5846673 Saidi et al. Dec 1998 A
5851504 Barker et al. Dec 1998 A
5853916 Venugopal et al. Dec 1998 A
5869207 Saidi et al. Feb 1999 A
5912093 Wen et al. Jun 1999 A
5916708 Besenhard et al. Jun 1999 A
5919587 Mukherjee et al. Jul 1999 A
5962169 Angell et al. Oct 1999 A
5998559 Narang et al. Dec 1999 A
6007947 Mayer Dec 1999 A
6013393 Taniuchi et al. Jan 2000 A
6015638 Ventura et al. Jan 2000 A
6030720 Chu et al. Feb 2000 A
6063899 Johnson et al. May 2000 A
6087426 Helms et al. Jul 2000 A
6096453 Grunwald Aug 2000 A
6103419 Saidi et al. Aug 2000 A
6103426 Narang et al. Aug 2000 A
6110619 Zhang et al. Aug 2000 A
6146787 Harrup et al. Nov 2000 A
6159640 Appel et al. Dec 2000 A
6168885 Narang et al. Jan 2001 B1
RE37076 Barker Feb 2001 E
6183718 Barker et al. Feb 2001 B1
6200707 Takada et al. Mar 2001 B1
6203949 Ehrlich Mar 2001 B1
6207326 Kawakami et al. Mar 2001 B1
6210831 Gorkovenko et al. Apr 2001 B1
6217623 Reichert et al. Apr 2001 B1
6223449 Johnson et al. May 2001 B1
6225009 Fleischer et al. May 2001 B1
6238821 Mukherjee et al. May 2001 B1
6287719 Bailey Sep 2001 B1
6306546 LaFleur et al. Oct 2001 B1
6312853 Zhang et al. Nov 2001 B1
6316141 Aurbach et al. Nov 2001 B1
6316149 Garbe et al. Nov 2001 B1
6328770 Gozdz Dec 2001 B1
6337101 Gozdz Jan 2002 B1
6337156 Narang et al. Jan 2002 B1
6341057 Nissen et al. Jan 2002 B1
6365300 Ota et al. Apr 2002 B1
6376123 Chu Apr 2002 B1
6379842 Mayer Apr 2002 B1
6379846 Terahara et al. Apr 2002 B1
6391492 Kawakami et al. May 2002 B1
6395423 Kawakami et al. May 2002 B1
6406814 Gorkovenko et al. Jun 2002 B1
6413675 Harada et al. Jul 2002 B1
6413676 Munshi Jul 2002 B1
6416905 Bronstert et al. Jul 2002 B1
6444370 Barker et al. Sep 2002 B2
6447952 Spiegel et al. Sep 2002 B1
6472104 Ulrich et al. Oct 2002 B1
6475679 Tsutiya et al. Nov 2002 B1
6475680 Arai et al. Nov 2002 B1
6482545 Skotheim et al. Nov 2002 B1
6489064 Appel et al. Dec 2002 B2
6492449 Michot et al. Dec 2002 B2
6495287 Kolb et al. Dec 2002 B1
6495289 Kawakami et al. Dec 2002 B1
6509122 Oyama Jan 2003 B1
6511769 Jung et al. Jan 2003 B1
6524737 Tanii et al. Feb 2003 B1
6541697 Georg et al. Apr 2003 B1
6544400 Hockaday et al. Apr 2003 B2
6544690 Harrup et al. Apr 2003 B1
6555026 Barker et al. Apr 2003 B1
6558850 Ehrlich May 2003 B2
6579643 Gozdz Jun 2003 B1
6596440 Gavelin et al. Jul 2003 B2
6599664 Ehrlich Jul 2003 B2
6605237 Allcock et al. Aug 2003 B2
6613475 Fauteux et al. Sep 2003 B2
6617078 Chia et al. Sep 2003 B1
6645675 Munshi Nov 2003 B1
6649033 Yagi et al. Nov 2003 B2
6664006 Munshi Dec 2003 B1
6667106 Kii et al. Dec 2003 B1
6673273 Ba Le et al. Jan 2004 B2
6677085 Appel et al. Jan 2004 B2
6682849 Narang et al. Jan 2004 B2
6699623 Dai Mar 2004 B1
6709785 Lee et al. Mar 2004 B2
6721168 Takeuchi et al. Apr 2004 B2
6723349 Hill et al. Apr 2004 B1
6726733 Lee et al. Apr 2004 B2
6730435 Nakane et al. May 2004 B1
6743549 Doyle et al. Jun 2004 B1
6746794 Mandal et al. Jun 2004 B2
6759164 Palazzo et al. Jul 2004 B2
6759460 Kamo et al. Jul 2004 B2
6790243 Vaidyanathan Sep 2004 B2
6794086 Dai et al. Sep 2004 B2
6797019 Takeuchi et al. Sep 2004 B2
6803151 Chen et al. Oct 2004 B2
6815119 Schmidt et al. Nov 2004 B2
6828065 Munshi Dec 2004 B2
6833218 Mann Dec 2004 B2
6841301 Heider et al. Jan 2005 B2
6869547 Barker et al. Mar 2005 B2
6878488 Gorkovenko et al. Apr 2005 B2
6893774 Schmidt et al. May 2005 B2
6908186 Zheng et al. Jun 2005 B2
6924061 Jow et al. Aug 2005 B1
6936761 Pichler Aug 2005 B2
6939647 Jow et al. Sep 2005 B1
6955867 Otsuki et al. Oct 2005 B1
6991876 Narang et al. Jan 2006 B2
7005206 Lawrence et al. Feb 2006 B2
7008564 Harrup et al. Mar 2006 B2
7052805 Narang et al. May 2006 B2
7060744 Murakami et al. Jun 2006 B2
7067219 Otsuki et al. Jun 2006 B2
7077516 Chen et al. Jul 2006 B2
7081320 Kawakami et al. Jul 2006 B2
7084290 Ignatyev et al. Aug 2006 B2
7091266 Murakami et al. Aug 2006 B2
7094501 Blau et al. Aug 2006 B2
7099142 Otsuki et al. Aug 2006 B2
7105254 Oyama Sep 2006 B2
7118694 Bronstert et al. Oct 2006 B2
7129005 Wensley et al. Oct 2006 B2
7192564 Cardarelli et al. Mar 2007 B2
7195840 Kaun Mar 2007 B2
7198865 Sloop Apr 2007 B2
7198870 Wensley et al. Apr 2007 B2
7211351 Klaassen May 2007 B2
7226702 Oh et al. Jun 2007 B2
7229719 Otsuki et al. Jun 2007 B2
7238450 Howard, Jr. et al. Jul 2007 B2
7238451 Frech et al. Jul 2007 B2
7241530 Oogami Jul 2007 B2
7247740 Schmidt et al. Jul 2007 B2
7253017 Roscheisen et al. Aug 2007 B1
7255965 Xu et al. Aug 2007 B2
7265379 Sandberg et al. Sep 2007 B2
7267908 Li et al. Sep 2007 B2
7270912 Oogami Sep 2007 B2
7273597 Takeuchi et al. Sep 2007 B2
7282295 Visco et al. Oct 2007 B2
7282296 Visco et al. Oct 2007 B2
7282297 Hisamitsu et al. Oct 2007 B2
7282302 Visco et al. Oct 2007 B2
7285362 Harrup et al. Oct 2007 B2
7291782 Sager et al. Nov 2007 B2
7295423 Mitchell et al. Nov 2007 B1
7316855 Lawrence et al. Jan 2008 B2
7342770 Mitchell et al. Mar 2008 B2
7344804 Klaassen Mar 2008 B2
7352558 Zhong et al. Apr 2008 B2
7377690 Diede May 2008 B1
7378193 Kang et al. May 2008 B2
7390591 Visco et al. Jun 2008 B2
7410731 Yoon et al. Aug 2008 B2
7429433 Otsuki et al. Sep 2008 B2
7442471 Jow et al. Oct 2008 B1
7452632 Lee et al. Nov 2008 B2
7473491 Amine et al. Jan 2009 B1
7476468 Lam et al. Jan 2009 B1
7491458 Visco et al. Feb 2009 B2
7494745 Kim et al. Feb 2009 B2
7498102 Oh et al. Mar 2009 B2
7507687 Kodas et al. Mar 2009 B2
7508651 Mitchell et al. Mar 2009 B2
7514180 Li Apr 2009 B2
7524439 Otsuki et al. Apr 2009 B2
7544445 Kinouchi et al. Jun 2009 B2
7553584 Chiang et al. Jun 2009 B2
7557637 Sakamoto Jul 2009 B2
7560595 Otsuki et al. Jul 2009 B2
7572554 Koike et al. Aug 2009 B2
7579112 Chiang et al. Aug 2009 B2
7579117 Beard Aug 2009 B1
7579118 Lee et al. Aug 2009 B2
7582380 Dunstan et al. Sep 2009 B1
7585587 Kanno et al. Sep 2009 B2
7585994 Ignatyev et al. Sep 2009 B2
7588859 Oh et al. Sep 2009 B1
7594982 Roscheisen et al. Sep 2009 B1
7598002 Gorkovenko et al. Oct 2009 B2
7604895 Kim et al. Oct 2009 B2
7608178 De Jonghe et al. Oct 2009 B2
7635530 Kenis et al. Dec 2009 B2
7645543 Visco et al. Jan 2010 B2
7656125 Lampe-Onnerud et al. Feb 2010 B2
7666233 Visco et al. Feb 2010 B2
7678505 Lee et al. Mar 2010 B2
7691289 Okun et al. Apr 2010 B2
7695860 Amine et al. Apr 2010 B2
7695862 Otsuki et al. Apr 2010 B2
7704468 Klaehn et al. Apr 2010 B1
7709158 Schlaikjer et al. May 2010 B1
7713449 Adachi et al. May 2010 B2
7718321 Yoon et al. May 2010 B2
7718826 Otsuki et al. May 2010 B2
7731765 Johnson Jun 2010 B2
7736806 Shimamura et al. Jun 2010 B2
7745047 Zhamu et al. Jun 2010 B2
7759418 Murakami et al. Jul 2010 B2
7771496 Nakahara et al. Aug 2010 B1
7771880 Kumar et al. Aug 2010 B2
7781098 Chiang et al. Aug 2010 B2
7781105 Lee et al. Aug 2010 B2
7781108 Visco et al. Aug 2010 B2
7790312 Costello et al. Sep 2010 B2
7790315 Mukherjee et al. Sep 2010 B2
7791861 Zhong et al. Sep 2010 B2
7811700 Hennige et al. Oct 2010 B2
7811707 Lampe-Onnerud et al. Oct 2010 B2
7811708 Lampe-Onnerud et al. Oct 2010 B2
7816032 Honda et al. Oct 2010 B2
7820328 Takeuchi et al. Oct 2010 B1
7824800 Dunstan et al. Nov 2010 B1
7828728 Boock et al. Nov 2010 B2
7829212 Visco et al. Nov 2010 B2
7829242 Horpel et al. Nov 2010 B2
7838143 Onnerud et al. Nov 2010 B2
7838144 Visco et al. Nov 2010 B2
7851090 Park et al. Dec 2010 B2
7858216 Sloop Dec 2010 B2
7858222 Hennige et al. Dec 2010 B2
7858223 Visco et al. Dec 2010 B2
7864397 Wu et al. Jan 2011 B2
7871721 Kim et al. Jan 2011 B2
7875204 Pan et al. Jan 2011 B2
7875393 Ryu et al. Jan 2011 B2
7883794 Kim et al. Feb 2011 B2
7887970 Gerald, II et al. Feb 2011 B1
7901830 Gerald, II et al. Mar 2011 B1
7919629 Michot Apr 2011 B2
7923801 Tian et al. Apr 2011 B2
7939198 Mukherjee et al. May 2011 B2
7939199 Gan et al. May 2011 B1
7939206 Otsuki et al. May 2011 B2
7951495 Otsuki et al. May 2011 B2
7960061 Jost et al. Jun 2011 B2
7965062 Kishi et al. Jun 2011 B2
7976983 Nakura Jul 2011 B2
7977393 Yoshimura Jul 2011 B2
7988746 Chiang et al. Aug 2011 B2
7989109 Lee et al. Aug 2011 B2
7993780 Jang et al. Aug 2011 B2
7993782 Takada et al. Aug 2011 B2
7998626 Visco et al. Aug 2011 B2
8000084 Siggel et al. Aug 2011 B2
8003241 Partin et al. Aug 2011 B2
8003256 Ohishi Aug 2011 B2
8004057 Tian et al. Aug 2011 B2
8007940 Marple et al. Aug 2011 B2
8012615 Onnerud et al. Sep 2011 B2
8013412 Tian Sep 2011 B2
8021775 Kaun Sep 2011 B2
8026008 Kim et al. Sep 2011 B2
8030500 Holenz et al. Oct 2011 B2
8034491 Ryu et al. Oct 2011 B2
8048569 Fujikawa et al. Nov 2011 B2
8048571 Visco et al. Nov 2011 B2
8057937 Sung et al. Nov 2011 B2
8062796 Yoon et al. Nov 2011 B2
8067107 Sloop et al. Nov 2011 B2
8071233 Partin et al. Dec 2011 B2
8072734 Zhong et al. Dec 2011 B2
8076031 West et al. Dec 2011 B1
8076032 West et al. Dec 2011 B1
8084998 Lampe-Onnerud et al. Dec 2011 B2
8092940 Tabuchi et al. Jan 2012 B2
8092942 Chen et al. Jan 2012 B1
8105733 Hoerpel et al. Jan 2012 B2
8114171 Visco et al. Feb 2012 B2
8119038 Lee et al. Feb 2012 B2
8119288 Zhamu et al. Feb 2012 B2
8124269 Takahashi et al. Feb 2012 B2
8124274 Marple et al. Feb 2012 B2
8129052 Visco et al. Mar 2012 B2
8133614 Gan et al. Mar 2012 B1
8137844 Awano et al. Mar 2012 B2
8138380 Olah et al. Mar 2012 B2
8148009 Chiang et al. Apr 2012 B2
8153307 Tanaka et al. Apr 2012 B1
8158282 Zhamu et al. Apr 2012 B2
8163204 Elliott et al. Apr 2012 B2
8163441 Hoerpel et al. Apr 2012 B2
8168326 Chiang et al. May 2012 B2
8168330 Tan et al. May 2012 B2
8168331 Best et al. May 2012 B2
8168831 Otsuki et al. May 2012 B2
8178009 Watanabe May 2012 B2
8178215 Yabe et al. May 2012 B2
8182943 Visco et al. May 2012 B2
8187749 Takahashi et al. May 2012 B2
8192863 Best et al. Jun 2012 B2
8202649 Visco et al. Jun 2012 B2
8206468 Chiang et al. Jun 2012 B2
8206469 Chiang et al. Jun 2012 B2
8211336 Miyasaka et al. Jul 2012 B2
8216722 Gordon Jul 2012 B2
8221915 Tikhonov et al. Jul 2012 B2
8227103 Tsukamoto Jul 2012 B2
8227105 Gerald, II et al. Jul 2012 B1
8227114 Tokita et al. Jul 2012 B2
8236446 Lu Aug 2012 B2
8236449 Nakura Aug 2012 B2
8241789 Chiang et al. Aug 2012 B2
8241793 Zhamu et al. Aug 2012 B2
8257866 Loveness et al. Sep 2012 B2
8257870 Horikawa Sep 2012 B2
8263248 Kaun Sep 2012 B2
8263697 Miyoshi et al. Sep 2012 B2
8268197 Singh et al. Sep 2012 B2
8269260 Tian et al. Sep 2012 B2
8269302 Tian et al. Sep 2012 B2
8274126 Tian et al. Sep 2012 B2
8277975 Chiang et al. Oct 2012 B2
8283071 Marple et al. Oct 2012 B2
8283325 Nam et al. Oct 2012 B2
8284539 Lu et al. Oct 2012 B2
8287483 Mitragotri et al. Oct 2012 B2
8293398 Visco et al. Oct 2012 B2
8301322 Mitsutani Oct 2012 B2
8308971 Bhat et al. Nov 2012 B1
8309240 Li et al. Nov 2012 B1
8318342 Ueda Nov 2012 B2
8323815 Beard Dec 2012 B2
8323820 Visco et al. Dec 2012 B2
8334075 Visco et al. Dec 2012 B2
8357450 Miyoshi et al. Jan 2013 B2
8357464 Sastry et al. Jan 2013 B2
8357468 Exnar et al. Jan 2013 B2
8361658 Shimamura et al. Jan 2013 B2
8361664 Visco et al. Jan 2013 B2
8367755 Terada Feb 2013 B2
8377586 Yazami Feb 2013 B2
8377596 Kaneko et al. Feb 2013 B2
8384058 Green Feb 2013 B2
8389147 Visco et al. Mar 2013 B2
8389173 Akiyama et al. Mar 2013 B2
8415045 Miyajima et al. Apr 2013 B2
8420266 Utsumi Apr 2013 B2
8426060 Hisamitsu et al. Apr 2013 B2
8435679 Lamanna et al. May 2013 B2
8441090 Tian et al. May 2013 B2
8445136 Visco et al. May 2013 B2
8450012 Cui et al. May 2013 B2
8455131 Visco et al. Jun 2013 B2
8455141 Nakamura et al. Jun 2013 B2
8459213 Moriarty et al. Jun 2013 B2
8465871 Juzkow et al. Jun 2013 B2
8466533 Tian et al. Jun 2013 B2
8470472 Nishie et al. Jun 2013 B2
8476727 Tian et al. Jul 2013 B2
8481195 Liu Jul 2013 B1
8482093 Tian et al. Jul 2013 B2
8486560 Tartaglia Jul 2013 B2
8486565 Hinago et al. Jul 2013 B2
8492023 Sastry et al. Jul 2013 B2
8492033 Amine et al. Jul 2013 B2
8501339 Visco et al. Aug 2013 B2
8512896 Ryu et al. Aug 2013 B2
8512899 Michot et al. Aug 2013 B2
8513758 Tian et al. Aug 2013 B2
8518525 Dennes et al. Aug 2013 B2
8524399 Kim et al. Sep 2013 B2
8525287 Tian et al. Sep 2013 B2
8529867 Fullerton Sep 2013 B2
8530099 Chen et al. Sep 2013 B2
8530940 Tian et al. Sep 2013 B2
8530991 Tian et al. Sep 2013 B2
8530992 Tian et al. Sep 2013 B2
8530993 Tian et al. Sep 2013 B2
8540899 Miller Sep 2013 B2
8541136 Beck et al. Sep 2013 B2
8546023 Park et al. Oct 2013 B2
8546853 Tian et al. Oct 2013 B2
8556996 Loveness et al. Oct 2013 B2
8557444 Arora et al. Oct 2013 B2
8558286 Tian et al. Oct 2013 B2
8562873 Murakami Oct 2013 B2
8574773 Wilson et al. Nov 2013 B2
8579994 Kawaoka et al. Nov 2013 B2
8580430 Chiang et al. Nov 2013 B2
8580432 Zhamu et al. Nov 2013 B2
8580438 Farmer et al. Nov 2013 B2
8586238 Chiang et al. Nov 2013 B2
8592075 Gerald, II et al. Nov 2013 B1
8592081 Utsumi Nov 2013 B2
8597815 Takahashi et al. Dec 2013 B2
8597827 Kako et al. Dec 2013 B2
8599534 Farahmandi Dec 2013 B2
8617736 Bhatt et al. Dec 2013 B2
8623543 Sastry et al. Jan 2014 B2
8623556 Liu Jan 2014 B1
8623964 Song et al. Jan 2014 B2
8628873 Kawasoe et al. Jan 2014 B2
8632898 Dougherty et al. Jan 2014 B2
8643064 Tian et al. Feb 2014 B2
8647773 Goodenough et al. Feb 2014 B2
8652686 Visco et al. Feb 2014 B2
8652688 Yushin et al. Feb 2014 B2
8652692 Visco et al. Feb 2014 B2
8658062 Kumta et al. Feb 2014 B2
8658304 Visco et al. Feb 2014 B2
8663841 Tajima et al. Mar 2014 B2
8669114 Sundermeyer et al. Mar 2014 B2
8671684 Moriarty Mar 2014 B2
8673477 Visco et al. Mar 2014 B2
8673499 Nakura Mar 2014 B2
8673503 Balaji et al. Mar 2014 B2
8679670 Onnerud et al. Mar 2014 B2
8679684 Kolosnitsyn et al. Mar 2014 B2
8679686 Patoux et al. Mar 2014 B2
8685569 Oguni et al. Apr 2014 B2
8686074 Tanji et al. Apr 2014 B2
8691444 Visco et al. Apr 2014 B2
8703310 Mullin et al. Apr 2014 B2
8703344 Bhat et al. Apr 2014 B2
8703345 Lee et al. Apr 2014 B2
8709531 Miller Apr 2014 B2
8709679 Visco et al. Apr 2014 B2
8715863 Zhang et al. May 2014 B2
8715865 Xu et al. May 2014 B2
8728170 Atanasoska et al. May 2014 B1
8734668 Bhat et al. May 2014 B2
8734674 Hersam et al. May 2014 B1
8734983 Kaun May 2014 B2
8734988 Palanichamy et al. May 2014 B2
8735005 Holstein et al. May 2014 B2
8741486 Jacobsen et al. Jun 2014 B1
8741500 Fujita et al. Jun 2014 B2
8748046 Smart et al. Jun 2014 B2
8754138 Michot et al. Jun 2014 B2
8758946 McDonald Jun 2014 B2
8764853 Xu et al. Jul 2014 B2
8765295 West et al. Jul 2014 B2
8765303 Chen et al. Jul 2014 B2
8765306 Amiruddin et al. Jul 2014 B2
8778522 Visco et al. Jul 2014 B2
8778533 Iwayasu et al. Jul 2014 B2
8778540 Farmer et al. Jul 2014 B1
8778546 Farmer Jul 2014 B2
8784694 Kay Jul 2014 B2
8785022 Sato et al. Jul 2014 B2
8785034 Forster et al. Jul 2014 B2
8786932 Copeland et al. Jul 2014 B2
8790814 Wang et al. Jul 2014 B2
8795886 Adachi et al. Aug 2014 B2
8795903 Smart et al. Aug 2014 B2
8801810 Cui et al. Aug 2014 B1
8802285 Ryu et al. Aug 2014 B2
8808924 Lee et al. Aug 2014 B2
8814956 Yamazaki Aug 2014 B2
8815432 Jo et al. Aug 2014 B2
8815443 Mitchell et al. Aug 2014 B2
8815453 Tsukamoto Aug 2014 B1
8822084 Tsujioka et al. Sep 2014 B2
8822088 Tajima et al. Sep 2014 B2
8828573 Visco et al. Sep 2014 B2
8828574 Visco et al. Sep 2014 B2
8828575 Visco et al. Sep 2014 B2
8828580 Visco et al. Sep 2014 B2
8828605 Lampe-Onnerud Sep 2014 B2
8841014 Deshpande et al. Sep 2014 B1
8841035 Choi et al. Sep 2014 B2
8845764 Kuriki Sep 2014 B2
8846249 Nakura Sep 2014 B2
8846251 Cui et al. Sep 2014 B2
8846922 Hoge et al. Sep 2014 B2
8852801 Takada et al. Oct 2014 B2
8852808 Arora et al. Oct 2014 B2
8852813 Madabusi et al. Oct 2014 B2
8858837 Oh et al. Oct 2014 B2
8859149 Nakamura Oct 2014 B2
8865355 Iriyama et al. Oct 2014 B2
8870810 Mitragotri et al. Oct 2014 B2
8871385 Gering et al. Oct 2014 B2
8871390 Balaji et al. Oct 2014 B2
8889285 Sastry et al. Nov 2014 B2
8889301 Balsara et al. Nov 2014 B2
8895189 Zhamu et al. Nov 2014 B2
8900754 Hinago et al. Dec 2014 B2
8906447 Zhamu et al. Dec 2014 B2
8906515 Tomantschger et al. Dec 2014 B2
8906548 Voelker et al. Dec 2014 B2
8906549 Palazzo Dec 2014 B1
8907133 Gellett et al. Dec 2014 B2
8911639 Lynd et al. Dec 2014 B2
8916291 Ichihashi et al. Dec 2014 B2
8922959 Cho et al. Dec 2014 B2
8927127 Hosoya et al. Jan 2015 B2
8927775 Rupert et al. Jan 2015 B2
8929054 Felten et al. Jan 2015 B2
8932771 Visco et al. Jan 2015 B2
8936882 Abraham et al. Jan 2015 B2
8940444 Gennett et al. Jan 2015 B2
8940446 Holme et al. Jan 2015 B1
8945774 Coowar et al. Feb 2015 B2
8951670 Alarco et al. Feb 2015 B2
8951673 Wessells et al. Feb 2015 B2
8951676 Doe et al. Feb 2015 B2
8962173 Liu Feb 2015 B1
8968820 Zhamu et al. Mar 2015 B2
8968921 Yazami Mar 2015 B2
8974947 Fujii et al. Mar 2015 B2
8980474 Kim et al. Mar 2015 B2
8980602 Medoff Mar 2015 B2
8981723 Sub Mar 2015 B2
8986638 Ivanovic-Burmazovic et al. Mar 2015 B2
8986881 Kako et al. Mar 2015 B2
8999008 Hudson et al. Apr 2015 B2
8999009 Tikhonov et al. Apr 2015 B2
9011731 Fu et al. Apr 2015 B2
9012093 Matsumoto et al. Apr 2015 B2
9012094 Tikhonov et al. Apr 2015 B2
9017879 Park et al. Apr 2015 B2
9029019 Jang et al. May 2015 B2
9029022 Miyagi et al. May 2015 B2
9034519 Xiao et al. May 2015 B2
9039788 Xu et al. May 2015 B2
9051629 Heres et al. Jun 2015 B2
9059477 Oh et al. Jun 2015 B2
9059481 He et al. Jun 2015 B2
9061261 Fullerton Jun 2015 B2
9065080 Sastry et al. Jun 2015 B2
9070948 Yu Jun 2015 B2
9076589 Wright et al. Jul 2015 B2
9076591 Zheng Jul 2015 B2
9077037 Hwu et al. Jul 2015 B2
9077046 Tikhonov et al. Jul 2015 B2
9093693 Zhamu et al. Jul 2015 B2
9093716 Tokuda et al. Jul 2015 B2
9093722 Zhang et al. Jul 2015 B2
9099252 Liu et al. Aug 2015 B2
9099738 Blomgren et al. Aug 2015 B2
9099756 Choi et al. Aug 2015 B2
9105908 Peuchert et al. Aug 2015 B2
9105942 Koga et al. Aug 2015 B2
9111684 Onagi et al. Aug 2015 B2
9112210 Chen et al. Aug 2015 B2
9112212 Fasching et al. Aug 2015 B1
9112236 Miyagi et al. Aug 2015 B2
9112239 Wu et al. Aug 2015 B2
9118088 Ohashi et al. Aug 2015 B2
9120121 Miller Sep 2015 B2
9123941 Visco et al. Sep 2015 B2
9123969 Sastry et al. Sep 2015 B2
9123973 Lee et al. Sep 2015 B2
9129754 Kuriki et al. Sep 2015 B2
9129756 Gadkaree et al. Sep 2015 B2
9130214 Wakayama et al. Sep 2015 B2
9130243 Nogi et al. Sep 2015 B2
9130245 Utsumi Sep 2015 B2
9130246 Han et al. Sep 2015 B2
9134547 McCabe et al. Sep 2015 B2
9136568 Visco et al. Sep 2015 B2
9142357 Matsumoto Sep 2015 B2
9147874 Chen et al. Sep 2015 B2
9147906 Tang et al. Sep 2015 B2
9166206 Kairawicz et al. Oct 2015 B2
9166222 Amiruddin et al. Oct 2015 B2
9166249 Darolles et al. Oct 2015 B2
9172076 Luski et al. Oct 2015 B2
9172088 Loveness et al. Oct 2015 B2
9172094 Loveness et al. Oct 2015 B2
9183994 Gadkaree et al. Nov 2015 B2
9183995 Inoue et al. Nov 2015 B2
9184467 Tikhonov et al. Nov 2015 B2
9184468 Tikhonov et al. Nov 2015 B2
9187834 Albrecht et al. Nov 2015 B2
9187835 Albrecht et al. Nov 2015 B2
9190616 Paulasaari et al. Nov 2015 B2
9190667 Zhamu et al. Nov 2015 B2
9190695 Okamoto et al. Nov 2015 B2
9190696 He et al. Nov 2015 B2
9190698 Smart et al. Nov 2015 B2
9196781 Tian et al. Nov 2015 B2
9196926 Kaneko et al. Nov 2015 B2
9200375 Gilliam et al. Dec 2015 B2
9203084 Wang et al. Dec 2015 B2
9203107 Kawasaki et al. Dec 2015 B2
9203113 Miyoshi et al. Dec 2015 B2
9206210 Gering et al. Dec 2015 B2
9207513 Milliron et al. Dec 2015 B2
9209446 Carlson Dec 2015 B2
9209456 Fasching et al. Dec 2015 B2
9214659 Horpel et al. Dec 2015 B2
9214696 Min et al. Dec 2015 B2
9219274 Kawasaki et al. Dec 2015 B2
9225003 Yukawa Dec 2015 B2
9225038 Hirose Dec 2015 B2
9227850 Ooishi Jan 2016 B2
9230746 Miyoshi et al. Jan 2016 B2
9231243 Cui et al. Jan 2016 B2
9236599 Zhong Jan 2016 B2
9236633 Chen et al. Jan 2016 B2
9236634 Cheng et al. Jan 2016 B2
9236635 Abe et al. Jan 2016 B2
9240614 Abe et al. Jan 2016 B2
9245691 Zheng Jan 2016 B1
9246150 Tsujikawa et al. Jan 2016 B2
9252399 Chamberlain, II et al. Feb 2016 B2
9252419 Miwa et al. Feb 2016 B2
9252422 Kim et al. Feb 2016 B2
9252455 Liu et al. Feb 2016 B1
9252456 Kofinas et al. Feb 2016 B2
9257720 Okamoto et al. Feb 2016 B2
9259690 Hanakawa et al. Feb 2016 B2
9263731 Tikhonov et al. Feb 2016 B2
9263764 Roh et al. Feb 2016 B2
9269961 Forster et al. Feb 2016 B2
9269998 Hayes et al. Feb 2016 B2
9273399 Hellring et al. Mar 2016 B2
9276268 Wieland Mar 2016 B2
9281541 Tokuda et al. Mar 2016 B2
9281543 Hosoya et al. Mar 2016 B2
9284264 Abbott et al. Mar 2016 B2
9284324 Nakamura et al. Mar 2016 B2
9287560 Yu Mar 2016 B2
9287573 Visco et al. Mar 2016 B2
9293236 Kawakami et al. Mar 2016 B2
9293749 Seo et al. Mar 2016 B2
9293773 Smart et al. Mar 2016 B2
9293787 Yawata et al. Mar 2016 B2
9293790 Doe et al. Mar 2016 B2
9293796 Lanning et al. Mar 2016 B2
9324992 Gennett et al. Apr 2016 B2
9325004 Chang et al. Apr 2016 B2
9331353 Chappey et al. May 2016 B2
9343741 Kitagawa et al. May 2016 B2
9350044 Kuriki et al. May 2016 B2
9350055 Sastry et al. May 2016 B2
20010004506 Gan et al. Jun 2001 A1
20010004507 Gan et al. Jun 2001 A1
20010010881 Ehrlich Aug 2001 A1
20010012590 Ehrlich Aug 2001 A1
20010033974 Gavelin et al. Oct 2001 A1
20010045364 Hockaday et al. Nov 2001 A1
20020014616 Allcock et al. Feb 2002 A1
20020018929 Dai et al. Feb 2002 A1
20020028387 Gavelin et al. Mar 2002 A1
20020031701 Kawakami et al. Mar 2002 A1
20020034692 Appel et al. Mar 2002 A1
20020034757 Cubicciotti Mar 2002 A1
20020039275 Takeuchi et al. Apr 2002 A1
20020042003 Appel et al. Apr 2002 A1
20020048706 Mayes et al. Apr 2002 A1
20020055040 Mukherjee et al. May 2002 A1
20020055047 Satoh et al. May 2002 A1
20020070374 Barker et al. Jun 2002 A1
20020074972 Narang et al. Jun 2002 A1
20020076611 Palazzo et al. Jun 2002 A1
20020085968 Smalley et al. Jul 2002 A1
20020086206 Fauteux et al. Jul 2002 A1
20020090331 Smalley et al. Jul 2002 A1
20020090547 Schmidt et al. Jul 2002 A1
20020094311 Smalley et al. Jul 2002 A1
20020098135 Smalley et al. Jul 2002 A1
20020100725 Lee et al. Aug 2002 A1
20020102196 Smalley et al. Aug 2002 A1
20020110739 McEwen et al. Aug 2002 A1
20020122979 Schmidt et al. Sep 2002 A1
20020122980 Fleischer et al. Sep 2002 A1
20020127162 Smalley et al. Sep 2002 A1
20020127169 Smalley et al. Sep 2002 A1
20020127454 Narang et al. Sep 2002 A1
20020128364 Michot et al. Sep 2002 A1
20020136681 Smalley et al. Sep 2002 A1
20020136683 Smalley et al. Sep 2002 A1
20020150524 Smalley et al. Oct 2002 A1
20020155353 Bronstert et al. Oct 2002 A1
20020159943 Smalley et al. Oct 2002 A1
20020160253 Vaidyanathan Oct 2002 A1
20020160257 Lee et al. Oct 2002 A1
20020160258 Lee et al. Oct 2002 A1
20020160270 Bronstert et al. Oct 2002 A1
20020160271 Frech et al. Oct 2002 A1
20020182488 Cho et al. Dec 2002 A1
20020185627 Chen-Yang et al. Dec 2002 A1
20020193533 Kamo et al. Dec 2002 A1
20020197522 Lawrence et al. Dec 2002 A1
20020197531 Inoue et al. Dec 2002 A1
20030003358 Mandal et al. Jan 2003 A1
20030003360 Gorkovenko et al. Jan 2003 A1
20030003369 Dai Jan 2003 A1
20030013007 Kaun Jan 2003 A1
20030014859 Kejha et al. Jan 2003 A1
20030031933 Shembel et al. Feb 2003 A1
20030038024 Yagi et al. Feb 2003 A1
20030059683 Blau et al. Mar 2003 A1
20030068555 Naruoka Apr 2003 A1
20030082446 Chiang et al. May 2003 A1
20030082458 Oyama May 2003 A1
20030091904 Munshi May 2003 A1
20030094599 Le et al. May 2003 A1
20030099884 Chiang et al. May 2003 A1
20030108801 Otsuki et al. Jun 2003 A1
20030113635 Gan et al. Jun 2003 A1
20030125437 Michot et al. Jul 2003 A1
20030129500 Gan et al. Jul 2003 A1
20030148191 Mori Aug 2003 A1
20030170548 Otsuki et al. Sep 2003 A1
20030175597 Otsuki et al. Sep 2003 A1
20030175598 Otsuki et al. Sep 2003 A1
20030180625 Oh et al. Sep 2003 A1
20030186110 Sloop Oct 2003 A1
20030190531 Otsuki et al. Oct 2003 A1
20030198868 Takeuchi et al. Oct 2003 A1
20030207178 Hu et al. Nov 2003 A1
20030211389 Schlaikjer Nov 2003 A1
20040009404 Harrup et al. Jan 2004 A1
20040013927 Lawrence et al. Jan 2004 A1
20040016455 Oogami Jan 2004 A1
20040028585 Cardarelli et al. Feb 2004 A1
20040036444 Oogami Feb 2004 A1
20040038122 Hisamitsu et al. Feb 2004 A1
20040038124 Hisamitsu et al. Feb 2004 A1
20040038127 Schlaikjer Feb 2004 A1
20040039134 Murakami et al. Feb 2004 A1
20040050414 Oogami Mar 2004 A1
20040053138 Otterstedt et al. Mar 2004 A1
20040072683 Kodas et al. Apr 2004 A1
20040084080 Sager et al. May 2004 A1
20040085710 Takeuchi et al. May 2004 A1
20040091772 Ravdel May 2004 A1
20040091774 Narang et al. May 2004 A1
20040126305 Chen et al. Jul 2004 A1
20040126658 Otsuki et al. Jul 2004 A1
20040126659 Graetz et al. Jul 2004 A1
20040139587 Sato et al. Jul 2004 A1
20040142246 Han et al. Jul 2004 A1
20040146778 Lee et al. Jul 2004 A1
20040146786 Sato et al. Jul 2004 A1
20040151985 Munshi Aug 2004 A1
20040157122 Naoi et al. Aug 2004 A1
20040158091 Ignatyev et al. Aug 2004 A1
20040170901 Blau et al. Sep 2004 A1
20040175622 Hu et al. Sep 2004 A9
20040189762 Chen et al. Sep 2004 A1
20040189763 Zheng et al. Sep 2004 A1
20040191617 Visco et al. Sep 2004 A1
20040191635 Otsuki et al. Sep 2004 A1
20040192853 Otsuki et al. Sep 2004 A1
20040201878 Agrawal et al. Oct 2004 A1
20040214090 West et al. Oct 2004 A1
20040218347 Schwake Nov 2004 A1
20040220348 Michot et al. Nov 2004 A1
20040229127 Wensley et al. Nov 2004 A1
20040234859 Lee et al. Nov 2004 A1
20040248014 West et al. Dec 2004 A1
20040253520 Wensley et al. Dec 2004 A1
20050008938 Cho et al. Jan 2005 A1
20050042503 Kim et al. Feb 2005 A1
20050042515 Hwang et al. Feb 2005 A1
20050053842 Young-Gyoon et al. Mar 2005 A1
20050085655 Schmidt et al. Apr 2005 A1
20050089890 Cubicciotti Apr 2005 A1
20050095197 Tuszynski et al. May 2005 A1
20050095504 Kim et al. May 2005 A1
20050095506 Klaassen May 2005 A1
20050106458 Eguchi et al. May 2005 A1
20050106460 Otsuki et al. May 2005 A1
20050106470 Yoon et al. May 2005 A1
20050118503 Honda et al. Jun 2005 A1
20050123836 Otsuki et al. Jun 2005 A1
20050136329 Howard, Jr. Jun 2005 A1
20050153207 Otsuki Jul 2005 A1
20050158626 Wagner et al. Jul 2005 A1
20050164093 Otsuki et al. Jul 2005 A1
20050170253 Yoon et al. Aug 2005 A1
20050170254 West et al. Aug 2005 A1
20050174092 Dougherty et al. Aug 2005 A1
20050175529 Ceder et al. Aug 2005 A1
20050175894 Visco et al. Aug 2005 A1
20050175895 Gorkovenko et al. Aug 2005 A1
20050175904 Gorkovenko Aug 2005 A1
20050181280 Ceder et al. Aug 2005 A1
20050186481 Ogawa et al. Aug 2005 A1
20050196672 Mukherjee et al. Sep 2005 A1
20050214700 Yamamoto et al. Sep 2005 A1
20050215764 Tuszynski et al. Sep 2005 A1
20050221168 Dahn et al. Oct 2005 A1
20050221192 Hennige et al. Oct 2005 A1
20050221193 Kinouchi et al. Oct 2005 A1
20050228087 Murakami et al. Oct 2005 A1
20050233207 Kim Oct 2005 A1
20050233212 Kaun Oct 2005 A1
20050233214 Marple et al. Oct 2005 A1
20050244704 Sloop et al. Nov 2005 A1
20050249656 Smalley et al. Nov 2005 A1
20050249667 Tuszynski et al. Nov 2005 A1
20050250011 Mitchell et al. Nov 2005 A1
20050250015 Wensley et al. Nov 2005 A1
20050255385 Harrup et al. Nov 2005 A1
20050260120 Smalley et al. Nov 2005 A1
20050266292 Kim et al. Dec 2005 A1
20050272214 Chiang et al. Dec 2005 A1
20050277023 Marple et al. Dec 2005 A1
20050287439 Shimamura et al. Dec 2005 A1
20060019131 Akiyama et al. Jan 2006 A1
20060019167 Li Jan 2006 A1
20060032046 Nathan et al. Feb 2006 A1
20060034943 Tuszynski Feb 2006 A1
20060035137 Maruo et al. Feb 2006 A1
20060035154 West et al. Feb 2006 A1
20060046151 Otsuki et al. Mar 2006 A1
20060073381 Kanno et al. Apr 2006 A1
20060078790 Nimon et al. Apr 2006 A1
20060088763 Li et al. Apr 2006 A1
20060105244 Kejha et al. May 2006 A1
20060109608 Zhong et al. May 2006 A1
20060112539 Kejha et al. Jun 2006 A1
20060115579 Mukherjee et al. Jun 2006 A1
20060121346 Nam et al. Jun 2006 A1
20060121355 Kolosnitsyn et al. Jun 2006 A1
20060137158 Zou et al. Jun 2006 A1
20060147371 Tuszynski et al. Jul 2006 A1
20060147795 Li et al. Jul 2006 A1
20060147807 Kim et al. Jul 2006 A1
20060154144 Gorkovenko et al. Jul 2006 A1
20060154147 Kurihara et al. Jul 2006 A1
20060159999 Kejha et al. Jul 2006 A1
20060166098 Tabuchi et al. Jul 2006 A1
20060172200 Yoon et al. Aug 2006 A1
20060174934 Sager et al. Aug 2006 A1
20060177740 Wensley et al. Aug 2006 A1
20060180796 Adachi et al. Aug 2006 A1
20060194119 Son et al. Aug 2006 A1
20060204834 Kim et al. Sep 2006 A1
20060204856 Ryu et al. Sep 2006 A1
20060204857 Kejha et al. Sep 2006 A1
20060210867 Kenis et al. Sep 2006 A1
20060210873 Hollenkamp et al. Sep 2006 A1
20060210883 Chen et al. Sep 2006 A1
20060216612 Jambunathan et al. Sep 2006 A1
20060217568 Ignatyev et al. Sep 2006 A1
20060228468 Lain et al. Oct 2006 A1
20060240327 Xu et al. Oct 2006 A1
20060246343 Mitchell et al. Nov 2006 A1
20060269834 West et al. Nov 2006 A1
20060281010 Lee et al. Dec 2006 A1
20060281011 Lee et al. Dec 2006 A1
20060292451 Lee et al. Dec 2006 A1
20070015053 Morris Jan 2007 A1
20070020529 Ryu et al. Jan 2007 A1
20070026315 Lampe-Onnerud et al. Feb 2007 A1
20070027129 Tuszynski et al. Feb 2007 A1
20070029972 Lampe-Onnerud et al. Feb 2007 A1
20070037046 Takahashi et al. Feb 2007 A1
20070037063 Choi et al. Feb 2007 A1
20070040154 Murakami Feb 2007 A1
20070042266 Oh et al. Feb 2007 A1
20070043158 Smalley et al. Feb 2007 A1
20070048209 Smalley et al. Mar 2007 A1
20070048596 Hasegawa et al. Mar 2007 A1
20070048622 Yoon et al. Mar 2007 A1
20070048623 Park et al. Mar 2007 A1
20070051620 Visco et al. Mar 2007 A1
20070054180 Miyajima et al. Mar 2007 A1
20070054186 Costello et al. Mar 2007 A1
20070065727 Koike et al. Mar 2007 A1
20070077496 Scott et al. Apr 2007 A1
20070085059 Mora-Gutierrez et al. Apr 2007 A1
20070092549 Tuszynski et al. Apr 2007 A1
20070092798 Spitler Apr 2007 A1
20070099072 Hennige et al. May 2007 A1
20070099084 Huang et al. May 2007 A1
20070099090 Oh et al. May 2007 A1
20070100012 Beard May 2007 A1
20070117007 Visco et al. May 2007 A1
20070117026 Kumar et al. May 2007 A1
20070122698 Mitchell et al. May 2007 A1
20070141470 Nakura Jun 2007 A1
20070146965 Mitchell et al. Jun 2007 A1
20070149496 Tuszynski et al. Jun 2007 A1
20070160901 Kaun Jul 2007 A1
20070166617 Gozdz et al. Jul 2007 A1
20070172739 Visco et al. Jul 2007 A1
20070172740 Otsuki et al. Jul 2007 A1
20070180688 Kawakami et al. Aug 2007 A1
20070181177 Sager et al. Aug 2007 A9
20070182418 Reynier et al. Aug 2007 A1
20070183954 Ohtsuki et al. Aug 2007 A1
20070190424 Mitchell et al. Aug 2007 A1
20070207384 Nakura Sep 2007 A1
20070212583 Johnson Sep 2007 A1
20070212615 Jost et al. Sep 2007 A1
20070216469 Sakamoto Sep 2007 A1
20070218370 Deguchi Sep 2007 A1
20070218371 Elliott et al. Sep 2007 A1
20070243454 Klaassen Oct 2007 A1
20070243470 Yamamoto et al. Oct 2007 A1
20070254213 Best et al. Nov 2007 A1
20070292746 Sloop Dec 2007 A1
20070292750 Beard Dec 2007 A1
20070298314 Partin et al. Dec 2007 A1
20080008928 Partin et al. Jan 2008 A1
20080008933 Lampe-Onnerud Jan 2008 A1
20080020276 Horikawa Jan 2008 A1
20080020284 Michot et al. Jan 2008 A1
20080020285 Horikawa Jan 2008 A1
20080026297 Chen et al. Jan 2008 A1
20080032197 Horpel et al. Feb 2008 A1
20080038641 Visco et al. Feb 2008 A1
20080044729 Gilmour Feb 2008 A1
20080044736 Nakura Feb 2008 A1
20080051495 Murakami et al. Feb 2008 A1
20080057386 Visco et al. Mar 2008 A1
20080063585 Smalley et al. Mar 2008 A1
20080063588 Smalley et al. Mar 2008 A1
20080066297 Lin et al. Mar 2008 A1
20080070076 Makita et al. Mar 2008 A1
20080075999 Izuhara et al. Mar 2008 A1
20080076023 Yumoto Mar 2008 A1
20080089830 Smalley et al. Apr 2008 A1
20080096056 Harrup et al. Apr 2008 A1
20080099734 Chiang et al. May 2008 A1
20080107586 Smalley et al. May 2008 A1
20080113266 Park et al. May 2008 A1
20080118428 Awano et al. May 2008 A1
20080118843 Tarnopolsky May 2008 A1
20080119421 Tuszynski et al. May 2008 A1
20080131772 Jambunathan et al. Jun 2008 A1
20080138700 Horpel et al. Jun 2008 A1
20080152996 Thackeray et al. Jun 2008 A1
20080153005 Horikawa et al. Jun 2008 A1
20080160417 Yoshimura Jul 2008 A1
20080164444 Otsuki et al. Jul 2008 A1
20080171263 Ugaji et al. Jul 2008 A1
20080171268 Yazami Jul 2008 A1
20080176141 Pan et al. Jul 2008 A1
20080193840 Shirane et al. Aug 2008 A1
20080193848 Fujikawa et al. Aug 2008 A1
20080193855 McDonald Aug 2008 A1
20080209876 Miller Sep 2008 A1
20080213588 Chen et al. Sep 2008 A1
20080213661 Michot et al. Sep 2008 A1
20080213662 Chiang et al. Sep 2008 A1
20080224100 Smalley et al. Sep 2008 A1
20080231237 Kishi et al. Sep 2008 A1
20080233477 Takahashi et al. Sep 2008 A1
20080241693 Fukuchi et al. Oct 2008 A1
20080241699 Halalay Oct 2008 A1
20080254361 Horikawa Oct 2008 A1
20080261116 Burton et al. Oct 2008 A1
20080269492 Otsuki et al. Oct 2008 A1
20080286649 Li et al. Nov 2008 A1
20080305401 Smart et al. Dec 2008 A1
20080311025 Smalley et al. Dec 2008 A1
20080318135 Sung et al. Dec 2008 A1
20090004094 Smalley et al. Jan 2009 A1
20090005824 Visco et al. Jan 2009 A1
20090011340 Lee et al. Jan 2009 A1
20090017364 Manev Jan 2009 A1
20090017386 Xu et al. Jan 2009 A1
20090023070 Tokita et al. Jan 2009 A1
20090023071 Ohishi Jan 2009 A1
20090027827 Siggel et al. Jan 2009 A1
20090029138 Miyoshi et al. Jan 2009 A1
20090029193 Onnerud et al. Jan 2009 A1
20090029237 Yazami Jan 2009 A1
20090035656 Lee et al. Feb 2009 A1
20090047579 Jang et al. Feb 2009 A1
20090075176 Singh et al. Mar 2009 A1
20090081547 Nakura Mar 2009 A1
20090081548 Nakura Mar 2009 A1
20090090640 Jang et al. Apr 2009 A1
20090104523 Mullin et al. Apr 2009 A1
20090117466 Zhamu et al. May 2009 A1
20090117467 Zhamu et al. May 2009 A1
20090123813 Chiang et al. May 2009 A1
20090130567 Segawa May 2009 A1
20090136830 Gordon May 2009 A1
20090136834 Coowar et al. May 2009 A1
20090136854 Nakura May 2009 A1
20090148771 Ishii et al. Jun 2009 A1
20090148777 Song et al. Jun 2009 A1
20090155696 Lee et al. Jun 2009 A1
20090155697 Park et al. Jun 2009 A1
20090169463 Smalley et al. Jul 2009 A1
20090169725 Zhamu et al. Jul 2009 A1
20090169996 Zhamu et al. Jul 2009 A1
20090178969 Hanakawa et al. Jul 2009 A1
20090181296 Lampe-Onnerud et al. Jul 2009 A1
20090186258 Makita et al. Jul 2009 A1
20090186267 Tiegs Jul 2009 A1
20090186276 Zhamu et al. Jul 2009 A1
20090186277 Beck et al. Jul 2009 A1
20090191464 Ryu et al. Jul 2009 A1
20090208832 Beard Aug 2009 A1
20090208835 Horiuchi et al. Aug 2009 A1
20090236973 Yabe et al. Sep 2009 A1
20090242830 Mao et al. Oct 2009 A1
20090246625 Lu Oct 2009 A1
20090246628 Adachi et al. Oct 2009 A1
20090253035 Otsuki et al. Oct 2009 A1
20090253046 Smart et al. Oct 2009 A1
20090256528 Greening et al. Oct 2009 A1
20090259420 Greening et al. Oct 2009 A1
20090269511 Zhamu et al. Oct 2009 A1
20090269654 Kairawicz et al. Oct 2009 A1
20090269673 Ignatyev et al. Oct 2009 A1
20090280400 Tsukamoto Nov 2009 A1
20090280414 Koh et al. Nov 2009 A1
20090286163 Shin et al. Nov 2009 A1
20090291330 Onnerud et al. Nov 2009 A1
20090292105 Michot Nov 2009 A1
20090297935 Visco et al. Dec 2009 A1
20090297937 Lampe-Onnerud et al. Dec 2009 A1
20090305016 Miyoshi et al. Dec 2009 A1
20090311587 Best et al. Dec 2009 A1
20090325017 Johnson Dec 2009 A9
20100000079 Horpel et al. Jan 2010 A1
20100003401 Horpel et al. Jan 2010 A1
20100003603 Chiang et al. Jan 2010 A1
20100009260 Tanaka et al. Jan 2010 A1
20100014215 Zhong et al. Jan 2010 A1
20100015514 Miyagi et al. Jan 2010 A1
20100015521 Kim Jan 2010 A1
20100018034 Miyasaka et al. Jan 2010 A1
20100021800 Yazami et al. Jan 2010 A1
20100021815 Oh et al. Jan 2010 A1
20100021819 Zhamu et al. Jan 2010 A1
20100028784 Pham et al. Feb 2010 A1
20100047695 Smart et al. Feb 2010 A1
20100062345 Horikawa Mar 2010 A1
20100068461 Wallace et al. Mar 2010 A1
20100068605 Harris et al. Mar 2010 A1
20100068628 Ueda Mar 2010 A1
20100075195 Elliott et al. Mar 2010 A1
20100075222 Watanabe Mar 2010 A1
20100075225 Wilkins et al. Mar 2010 A1
20100078599 Kumta et al. Apr 2010 A1
20100086823 Koshino et al. Apr 2010 A1
20100090650 Yazami et al. Apr 2010 A1
20100092869 Kaneko et al. Apr 2010 A1
20100094042 Klaehn et al. Apr 2010 A1
20100099031 Katu et al. Apr 2010 A1
20100104950 Lamanna et al. Apr 2010 A1
20100112443 Blomgren et al. May 2010 A1
20100119881 Patel et al. May 2010 A1
20100119883 Friesen et al. May 2010 A1
20100119956 Tokuda et al. May 2010 A1
20100120179 Zhamu et al. May 2010 A1
20100124691 Harris May 2010 A1
20100125082 Holenz et al. May 2010 A1
20100125087 Holenz et al. May 2010 A1
20100136410 Kawasoe et al. Jun 2010 A1
20100143770 Onnerud et al. Jun 2010 A1
20100143798 Zhamu et al. Jun 2010 A1
20100151303 Marple et al. Jun 2010 A1
20100159346 Hinago et al. Jun 2010 A1
20100164436 Lampe-Onnerud et al. Jul 2010 A1
20100166961 Beard Jul 2010 A1
20100167121 Arai et al. Jul 2010 A1
20100167129 Wu et al. Jul 2010 A1
20100173139 Miyoshi et al. Jul 2010 A1
20100173198 Zhamu et al. Jul 2010 A1
20100176337 Zhamu et al. Jul 2010 A1
20100178531 Amaratunga et al. Jul 2010 A1
20100178555 Best Jul 2010 A1
20100178562 Exnar et al. Jul 2010 A1
20100178567 Hauser et al. Jul 2010 A1
20100178568 Unalan et al. Jul 2010 A1
20100180889 Monzyk et al. Jul 2010 A1
20100183907 Hauser et al. Jul 2010 A1
20100183917 Holzapfel et al. Jul 2010 A1
20100190059 Graetz et al. Jul 2010 A1
20100193370 Olah et al. Aug 2010 A1
20100196766 Park et al. Aug 2010 A1
20100200403 Lopatin et al. Aug 2010 A1
20100203370 Pozin et al. Aug 2010 A1
20100209782 Choi et al. Aug 2010 A1
20100210745 McDaniel et al. Aug 2010 A1
20100216016 Seino et al. Aug 2010 A1
20100216023 Wei et al. Aug 2010 A1
20100216027 Fujii Aug 2010 A1
20100216033 Shimamura et al. Aug 2010 A1
20100224824 Gorshkov Sep 2010 A1
20100233523 Jo et al. Sep 2010 A1
20100239902 Hisamitsu et al. Sep 2010 A1
20100239917 Lee et al. Sep 2010 A1
20100240813 Terada Sep 2010 A1
20100248078 Beard Sep 2010 A1
20100255356 Fujii et al. Oct 2010 A1
20100255383 Kofinas et al. Oct 2010 A1
20100263201 Hisamitsu et al. Oct 2010 A1
20100263910 Mitchell et al. Oct 2010 A1
20100279155 Scott et al. Nov 2010 A1
20100285352 Juzkow et al. Nov 2010 A1
20100285354 Su et al. Nov 2010 A1
20100285358 Cui et al. Nov 2010 A1
20100285373 Horikawa Nov 2010 A1
20100291293 Hennige et al. Nov 2010 A1
20100291429 Farmer Nov 2010 A1
20100291443 Farmer Nov 2010 A1
20100291444 Farmer et al. Nov 2010 A1
20100293779 Kim et al. Nov 2010 A1
20100297502 Zhu et al. Nov 2010 A1
20100297510 Kim et al. Nov 2010 A1
20100299008 Mitsutani Nov 2010 A1
20100304205 Jo et al. Dec 2010 A1
20100304223 Otsuki et al. Dec 2010 A1
20100310941 Kumta et al. Dec 2010 A1
20100320089 Misra et al. Dec 2010 A1
20100323238 Takahashi et al. Dec 2010 A1
20100330410 Takahashi et al. Dec 2010 A1
20100330419 Cui et al. Dec 2010 A1
20100330421 Cui et al. Dec 2010 A1
20100330423 Cui et al. Dec 2010 A1
20100330425 Lopatin et al. Dec 2010 A1
20100330433 Amine et al. Dec 2010 A1
20110003213 Burchardt et al. Jan 2011 A1
20110005065 Chiang et al. Jan 2011 A1
20110012067 Kay Jan 2011 A1
20110014279 Mora-Gutierrez et al. Jan 2011 A1
20110014522 Visco et al. Jan 2011 A1
20110014523 Park et al. Jan 2011 A1
20110014527 Ohlsen Jan 2011 A1
20110020704 Fukuchi et al. Jan 2011 A1
20110020706 Nesper Jan 2011 A1
20110024396 Onnerud et al. Feb 2011 A1
20110027656 Chiang et al. Feb 2011 A1
20110033734 Chamberlain et al. Feb 2011 A1
20110033756 Nakura Feb 2011 A1
20110039144 Visco et al. Feb 2011 A1
20110039157 Sasaki et al. Feb 2011 A1
20110045346 Chiang et al. Feb 2011 A1
20110049745 Katayama et al. Mar 2011 A1
20110052966 Lampe-Onnerud Mar 2011 A1
20110059349 Lampe-Onnerud et al. Mar 2011 A1
20110064988 Yu Mar 2011 A1
20110064999 Chiang et al. Mar 2011 A1
20110067230 Tan et al. Mar 2011 A1
20110070489 Chiang et al. Mar 2011 A1
20110070495 Ban et al. Mar 2011 A1
20110070504 Matsumoto et al. Mar 2011 A1
20110076542 Farmer Mar 2011 A1
20110076572 Amine et al. Mar 2011 A1
20110077880 Gering Mar 2011 A1
20110081563 Christensen et al. Apr 2011 A1
20110081575 Voelker et al. Apr 2011 A1
20110081581 Ryu et al. Apr 2011 A1
20110086781 Smalley et al. Apr 2011 A1
20110097624 Bhatt et al. Apr 2011 A1
20110097628 Lopatin et al. Apr 2011 A1
20110097630 Choi et al. Apr 2011 A1
20110098463 Yoshitani et al. Apr 2011 A1
20110104553 Pol et al. May 2011 A1
20110104565 Utsumi May 2011 A1
20110111294 Lopez et al. May 2011 A1
20110111304 Cui et al. May 2011 A1
20110114896 Mitchell et al. May 2011 A1
20110117407 Huang May 2011 A1
20110117445 Abraham May 2011 A1
20110117446 Lucht et al. May 2011 A1
20110123869 Choi et al. May 2011 A1
20110136006 Nogi et al. Jun 2011 A1
20110136019 Amiruddin et al. Jun 2011 A1
20110139331 Arora et al. Jun 2011 A1
20110139730 Dennes et al. Jun 2011 A1
20110143201 Takada et al. Jun 2011 A1
20110143202 Farmer et al. Jun 2011 A1
20110143207 Arora et al. Jun 2011 A1
20110143217 Arora et al. Jun 2011 A1
20110143219 Weiss et al. Jun 2011 A1
20110151324 Chiang et al. Jun 2011 A1
20110159329 Tsujikawa et al. Jun 2011 A1
20110159365 Loveness et al. Jun 2011 A1
20110159366 Nakura Jun 2011 A1
20110159377 Lee et al. Jun 2011 A1
20110159379 Matsumoto et al. Jun 2011 A1
20110171502 Kottenstette et al. Jul 2011 A1
20110171539 Patoux et al. Jul 2011 A1
20110177393 Park et al. Jul 2011 A1
20110178306 Michot Jul 2011 A1
20110181249 Deguchi et al. Jul 2011 A1
20110183216 Kim et al. Jul 2011 A1
20110189512 Onnerud et al. Aug 2011 A1
20110189520 Carter et al. Aug 2011 A1
20110189548 Xu Aug 2011 A1
20110189579 Bismarck et al. Aug 2011 A1
20110195318 Tsujikawa et al. Aug 2011 A1
20110200874 Ono et al. Aug 2011 A1
20110206979 Giroud et al. Aug 2011 A1
20110206994 Balsara et al. Aug 2011 A1
20110207000 Jow et al. Aug 2011 A1
20110212359 Dai et al. Sep 2011 A1
20110229761 Cui et al. Sep 2011 A1
20110236751 Amiruddin et al. Sep 2011 A1
20110236765 Matsui et al. Sep 2011 A1
20110236772 Burchardt et al. Sep 2011 A1
20110236798 Burchardt et al. Sep 2011 A1
20110236799 Burchardt et al. Sep 2011 A1
20110240064 Wales et al. Oct 2011 A1
20110244313 Holstein et al. Oct 2011 A1
20110250503 Wilson et al. Oct 2011 A1
20110250626 Williams et al. Oct 2011 A1
20110256457 Utsumi Oct 2011 A1
20110264381 Gering Oct 2011 A1
20110269010 Sawaguchi et al. Nov 2011 A1
20110274976 Blomgren et al. Nov 2011 A1
20110274977 Nakura Nov 2011 A1
20110278170 Chiang et al. Nov 2011 A1
20110281159 Farmer et al. Nov 2011 A1
20110287316 Lu et al. Nov 2011 A1
20110287318 Loveness et al. Nov 2011 A1
20110293997 Tartaglia Dec 2011 A1
20110300444 Nakamura Dec 2011 A1
20110300450 Balaji et al. Dec 2011 A1
20110301931 Gering Dec 2011 A1
20110305949 Nesper et al. Dec 2011 A1
20110305958 Kuriki Dec 2011 A1
20110311865 Tatsumi et al. Dec 2011 A1
20110311881 Benicewicz Dec 2011 A1
20110319426 Holenz et al. Dec 2011 A1
20120003508 Narbonne et al. Jan 2012 A1
20120003514 Tsujikawa et al. Jan 2012 A1
20120003518 Fischel Jan 2012 A1
20120007560 Smart et al. Jan 2012 A1
20120009481 Song et al. Jan 2012 A1
20120009483 Chu et al. Jan 2012 A1
20120009485 Zu et al. Jan 2012 A1
20120015249 Awano et al. Jan 2012 A1
20120021266 Marple et al. Jan 2012 A1
20120021286 Tabuchi et al. Jan 2012 A1
20120021294 Zhamu et al. Jan 2012 A1
20120021303 Amendola et al. Jan 2012 A1
20120028105 Kumar et al. Feb 2012 A1
20120034500 Kaun Feb 2012 A1
20120034512 Zhang et al. Feb 2012 A1
20120034523 Sheem et al. Feb 2012 A1
20120038967 Copeland et al. Feb 2012 A1
20120045670 Stefan et al. Feb 2012 A1
20120045697 Park et al. Feb 2012 A1
20120052401 Goodenough et al. Mar 2012 A1
20120058377 Sastry et al. Mar 2012 A1
20120058398 Balaji et al. Mar 2012 A1
20120060360 Liu Mar 2012 A1
20120064396 Nishie et al. Mar 2012 A1
20120064398 Kim et al. Mar 2012 A1
20120064399 Carlson Mar 2012 A1
20120064409 Zhamu et al. Mar 2012 A1
20120070741 Liu et al. Mar 2012 A1
20120077076 Cheng et al. Mar 2012 A1
20120077082 Se-Hee et al. Mar 2012 A1
20120077091 Lee et al. Mar 2012 A1
20120082873 Fischel Apr 2012 A1
20120082890 Dong et al. Apr 2012 A1
20120082901 Schmidt et al. Apr 2012 A1
20120082902 Hwu et al. Apr 2012 A1
20120082903 Zhang et al. Apr 2012 A1
20120088155 Yushin et al. Apr 2012 A1
20120088162 Harrup et al. Apr 2012 A1
20120094178 Loveridge et al. Apr 2012 A1
20120094188 Visco et al. Apr 2012 A1
20120094194 Visco et al. Apr 2012 A1
20120097194 McDaniel et al. Apr 2012 A1
20120100438 Fasching et al. Apr 2012 A1
20120105007 Amiruddin et al. May 2012 A1
20120107680 Amiruddin et al. May 2012 A1
20120107697 Roh et al. May 2012 A1
20120107726 Ogata et al. May 2012 A1
20120110835 Hudson et al. May 2012 A1
20120115018 Kawaoka et al. May 2012 A1
20120115041 West et al. May 2012 A1
20120121974 Tikhonov et al. May 2012 A1
20120121989 Roberts et al. May 2012 A1
20120121991 Tikhonov et al. May 2012 A1
20120129019 Onnerud et al. May 2012 A1
20120129045 Gin et al. May 2012 A1
20120129046 Utsumi May 2012 A1
20120133341 Gan et al. May 2012 A1
20120135312 Takahashi May 2012 A1
20120135313 West et al. May 2012 A1
20120141864 Juzkow et al. Jun 2012 A1
20120141866 Kuriki et al. Jun 2012 A1
20120141867 Iwayasu et al. Jun 2012 A1
20120141869 Takahata Jun 2012 A1
20120141870 Chen et al. Jun 2012 A1
20120141878 Ohashi et al. Jun 2012 A1
20120141883 Smart et al. Jun 2012 A1
20120141884 Takahata Jun 2012 A1
20120148896 Dennes et al. Jun 2012 A1
20120148897 Dennes et al. Jun 2012 A1
20120148922 Takahashi Jun 2012 A1
20120149852 Dennes et al. Jun 2012 A1
20120155507 Srinivasan et al. Jun 2012 A1
20120164519 Lee et al. Jun 2012 A1
20120164541 Darolles et al. Jun 2012 A1
20120169297 Schaefer et al. Jul 2012 A1
20120171535 Ma Jul 2012 A1
20120171536 Kaneda Jul 2012 A1
20120171542 Matsumoto et al. Jul 2012 A1
20120175552 Fukuchi et al. Jul 2012 A1
20120177995 Sun et al. Jul 2012 A1
20120178145 Nam et al. Jul 2012 A1
20120183842 Kawasaki et al. Jul 2012 A1
20120183843 Kawasaki et al. Jul 2012 A1
20120183856 Cui et al. Jul 2012 A1
20120183865 Deguchi Jul 2012 A1
20120183866 Lee et al. Jul 2012 A1
20120188086 Xie et al. Jul 2012 A1
20120189910 Brune et al. Jul 2012 A1
20120189920 Li et al. Jul 2012 A1
20120202112 Yushin et al. Aug 2012 A1
20120208087 Yamamoto et al. Aug 2012 A1
20120218683 Kondou et al. Aug 2012 A1
20120219865 Kaneko et al. Aug 2012 A1
20120225331 Tartaglia Sep 2012 A1
20120225358 Seo et al. Sep 2012 A1
20120225359 Xu et al. Sep 2012 A1
20120231308 Chiang et al. Sep 2012 A1
20120231325 Yoon et al. Sep 2012 A1
20120231336 Kim et al. Sep 2012 A1
20120231352 Pol et al. Sep 2012 A1
20120232285 Michot Sep 2012 A1
20120244391 Yushin et al. Sep 2012 A1
20120244417 Takahata et al. Sep 2012 A1
20120249080 Sub Oct 2012 A1
20120251886 Yushin et al. Oct 2012 A1
20120251892 Kang et al. Oct 2012 A1
20120251896 Chiang et al. Oct 2012 A1
20120270076 Yazami Oct 2012 A9
20120270112 Visco et al. Oct 2012 A1
20120273737 Ooishi Nov 2012 A1
20120276445 Xu Nov 2012 A1
20120282530 Chiang et al. Nov 2012 A1
20120288750 Kung et al. Nov 2012 A1
20120288751 Kako et al. Nov 2012 A1
20120288769 Kono et al. Nov 2012 A1
20120289887 Visco et al. Nov 2012 A1
20120292196 Albrecht et al. Nov 2012 A1
20120292197 Albrecht et al. Nov 2012 A1
20120293916 Lee et al. Nov 2012 A1
20120295155 Deng et al. Nov 2012 A1
20120295165 Morin et al. Nov 2012 A1
20120295166 Gennett et al. Nov 2012 A1
20120297611 Ma Nov 2012 A1
20120301789 Loveness et al. Nov 2012 A1
20120301797 Abe et al. Nov 2012 A1
20120308894 Oguni et al. Dec 2012 A1
20120315535 Matsumoto Dec 2012 A1
20120315546 Kaneko et al. Dec 2012 A1
20120315549 Tang et al. Dec 2012 A1
20120321959 Yushin et al. Dec 2012 A1
20120323036 Chen et al. Dec 2012 A1
20120326073 Lynd et al. Dec 2012 A1
20120328942 Thomas-Alyea et al. Dec 2012 A1
20120328952 Yushin et al. Dec 2012 A1
20130001092 Abbott et al. Jan 2013 A1
20130004839 Utsumi Jan 2013 A1
20130004852 Visco et al. Jan 2013 A1
20130004859 Yu et al. Jan 2013 A1
20130004862 Miyoshi et al. Jan 2013 A1
20130011728 Tokuda et al. Jan 2013 A1
20130011736 Loveness et al. Jan 2013 A1
20130017443 Yamazaki Jan 2013 A1
20130017453 Ajayan et al. Jan 2013 A1
20130020557 Roscheisen et al. Jan 2013 A1
20130022861 Miyagi et al. Jan 2013 A1
20130022863 Madabusi et al. Jan 2013 A1
20130022880 Tsujioka et al. Jan 2013 A1
20130026409 Baker et al. Jan 2013 A1
20130029232 Zheng et al. Jan 2013 A1
20130034762 Marple et al. Feb 2013 A1
20130040203 Yoon et al. Feb 2013 A1
20130043057 Oguni et al. Feb 2013 A1
20130043125 Gill et al. Feb 2013 A1
20130043843 Amiruddin et al. Feb 2013 A1
20130045427 Zhamu et al. Feb 2013 A1
20130048923 Gorshkov Feb 2013 A1
20130052508 Kim et al. Feb 2013 A1
20130052528 Kuriki et al. Feb 2013 A1
20130052542 Abraham et al. Feb 2013 A1
20130055559 Slocum et al. Mar 2013 A1
20130059172 Sastry et al. Mar 2013 A1
20130059195 Kuriki et al. Mar 2013 A1
20130065122 Chiang et al. Mar 2013 A1
20130065130 Ban et al. Mar 2013 A1
20130067726 Kuriki et al. Mar 2013 A1
20130069601 Coowar et al. Mar 2013 A1
20130069658 Rich et al. Mar 2013 A1
20130069661 Rich et al. Mar 2013 A1
20130070391 Zheng Mar 2013 A1
20130071733 Abe et al. Mar 2013 A1
20130071739 Tajima et al. Mar 2013 A1
20130071762 Tajima et al. Mar 2013 A1
20130072154 Rich et al. Mar 2013 A1
20130078525 Morin et al. Mar 2013 A1
20130084495 Tajima et al. Apr 2013 A1
20130084496 Osada et al. Apr 2013 A1
20130084501 Ivakayama et al. Apr 2013 A1
20130084505 Iriyama et al. Apr 2013 A1
20130088204 Khare et al. Apr 2013 A1
20130089793 Gering et al. Apr 2013 A1
20130090900 Gering Apr 2013 A1
20130092866 Rupert et al. Apr 2013 A1
20130095351 Gellett et al. Apr 2013 A1
20130095392 Shin et al. Apr 2013 A1
20130100563 Cho et al. Apr 2013 A1
20130108539 Fu et al. May 2013 A1
20130108802 Oladeji May 2013 A1
20130108899 Schaefer May 2013 A1
20130108920 Oladeji May 2013 A1
20130108930 Patterson et al. May 2013 A1
20130115520 Abe et al. May 2013 A1
20130115529 Zhang et al. May 2013 A1
20130115531 Amendola et al. May 2013 A1
20130122361 Yazami May 2013 A1
20130128488 Forster et al. May 2013 A1
20130130069 Mullin et al. May 2013 A1
20130130108 Alarco et al. May 2013 A1
20130130121 Abe et al. May 2013 A1
20130130125 Hauser May 2013 A1
20130130126 McDonald et al. May 2013 A1
20130130128 Okamoto et al. May 2013 A1
20130135110 Xie et al. May 2013 A1
20130136981 Peuchert et al. May 2013 A1
20130141693 McCabe et al. Jun 2013 A1
20130143090 Hosoya et al. Jun 2013 A1
20130143129 Okamoto et al. Jun 2013 A1
20130149567 Schaefer Jun 2013 A1
20130149596 Shiflett Jun 2013 A1
20130149602 Luski et al. Jun 2013 A1
20130149605 Kakehata et al. Jun 2013 A1
20130157141 Zhong et al. Jun 2013 A1
20130157147 Li et al. Jun 2013 A1
20130157149 Peled et al. Jun 2013 A1
20130157152 Lanning et al. Jun 2013 A1
20130163148 Isii et al. Jun 2013 A1
20130164571 Hirose Jun 2013 A1
20130164611 Nanba et al. Jun 2013 A1
20130164612 Tanemura et al. Jun 2013 A1
20130164628 Visco et al. Jun 2013 A1
20130167363 Xu et al. Jul 2013 A1
20130169238 Rojeski Jul 2013 A1
20130171340 Rojeski Jul 2013 A1
20130171500 Xu et al. Jul 2013 A1
20130171502 Chen et al. Jul 2013 A1
20130171512 Rojeski Jul 2013 A1
20130177814 Rojeski et al. Jul 2013 A1
20130177818 Han et al. Jul 2013 A1
20130178011 Ginley et al. Jul 2013 A1
20130183579 Kim et al. Jul 2013 A1
20130183580 Kako et al. Jul 2013 A1
20130189575 Anguchamy et al. Jul 2013 A1
20130189579 Darby et al. Jul 2013 A1
20130194723 Felten et al. Aug 2013 A1
20130195805 Wei et al. Aug 2013 A1
20130196223 Gering et al. Aug 2013 A1
20130196235 Prieto et al. Aug 2013 A1
20130199936 Zhang et al. Aug 2013 A1
20130202920 Xu et al. Aug 2013 A1
20130202945 Zhamu et al. Aug 2013 A1
20130202955 Yawata et al. Aug 2013 A1
20130202956 Xu et al. Aug 2013 A1
20130202959 Chiang et al. Aug 2013 A1
20130202967 Kim et al. Aug 2013 A1
20130202973 Lane et al. Aug 2013 A1
20130206606 Gilliam et al. Aug 2013 A1
20130209348 Ludvik et al. Aug 2013 A1
20130209860 Tsujikawa et al. Aug 2013 A1
20130209869 Rojeski Aug 2013 A1
20130209870 Tsujikawa et al. Aug 2013 A1
20130209887 Young Aug 2013 A1
20130209897 Paranthaman et al. Aug 2013 A1
20130216894 Wang et al. Aug 2013 A1
20130216899 Tsujikawa et al. Aug 2013 A1
20130216907 Rayner et al. Aug 2013 A1
20130216908 Tsujikawa et al. Aug 2013 A1
20130216918 Tokuda et al. Aug 2013 A1
20130216920 Tsujikawa et al. Aug 2013 A1
20130224576 Rosciano et al. Aug 2013 A1
20130224583 Green Aug 2013 A1
20130224603 Chen et al. Aug 2013 A1
20130224604 Yu et al. Aug 2013 A1
20130224605 Lamanna et al. Aug 2013 A1
20130230772 Noda et al. Sep 2013 A1
20130230773 Tsujikawa et al. Sep 2013 A1
20130230779 Kaneko et al. Sep 2013 A1
20130232772 Tikhonov et al. Sep 2013 A1
20130234074 Gilles et al. Sep 2013 A1
20130236750 Sato Sep 2013 A1
20130236766 Seo et al. Sep 2013 A1
20130244095 Min et al. Sep 2013 A1
20130244102 Golodnitsky et al. Sep 2013 A1
20130244107 Rojeski Sep 2013 A1
20130244133 Wieland Sep 2013 A1
20130252090 Tsujikawa et al. Sep 2013 A1
20130252101 Zhou et al. Sep 2013 A1
20130252112 Doe et al. Sep 2013 A1
20130252114 Doe et al. Sep 2013 A1
20130259776 Heres et al. Oct 2013 A1
20130260222 Lu et al. Oct 2013 A1
20130260229 Uzun et al. Oct 2013 A1
20130260232 Lu et al. Oct 2013 A1
20130260246 Chen et al. Oct 2013 A1
20130260254 Kren et al. Oct 2013 A1
20130260255 Lopatin et al. Oct 2013 A1
20130264999 Srinivasan et al. Oct 2013 A1
20130266827 Sastry et al. Oct 2013 A1
20130266846 Kawasaki et al. Oct 2013 A1
20130266858 Inoue et al. Oct 2013 A1
20130266866 Miyazaki et al. Oct 2013 A1
20130271085 Chen et al. Oct 2013 A1
20130271089 Yazami et al. Oct 2013 A1
20130277599 Michot et al. Oct 2013 A1
20130280579 Wright et al. Oct 2013 A1
20130280592 Sato et al. Oct 2013 A1
20130280601 Geramita et al. Oct 2013 A1
20130280621 Koga et al. Oct 2013 A1
20130288083 Sweetland et al. Oct 2013 A1
20130288084 Sastry et al. Oct 2013 A1
20130288113 Onagi et al. Oct 2013 A1
20130288120 Iida et al. Oct 2013 A1
20130288136 Arora et al. Oct 2013 A1
20130288138 Tikhonov et al. Oct 2013 A1
20130295439 Masarapu et al. Nov 2013 A1
20130295461 Chen et al. Nov 2013 A1
20130295465 Kaneko et al. Nov 2013 A1
20130295492 Hinago et al. Nov 2013 A1
20130302650 Delangis Nov 2013 A1
20130302679 Uemachi Nov 2013 A1
20130302697 Wang et al. Nov 2013 A1
20130302702 Matsumoto Nov 2013 A1
20130302704 Visco et al. Nov 2013 A1
20130309527 Liu et al. Nov 2013 A1
20130309549 Luski et al. Nov 2013 A1
20130309561 Chen et al. Nov 2013 A1
20130309564 Yoshida et al. Nov 2013 A1
20130309571 Yoon et al. Nov 2013 A1
20130309580 Tomura Nov 2013 A1
20130316233 Hirayama et al. Nov 2013 A1
20130316248 Ignatyev et al. Nov 2013 A9
20130319870 Chen et al. Dec 2013 A1
20130320582 Cui et al. Dec 2013 A1
20130320928 Yazami et al. Dec 2013 A1
20130323571 Dai et al. Dec 2013 A1
20130323585 Inoue et al. Dec 2013 A1
20130323595 Sohn et al. Dec 2013 A1
20130323605 Yamamoto et al. Dec 2013 A1
20130327648 Grant et al. Dec 2013 A1
20130330609 Sawa et al. Dec 2013 A1
20130330611 Chen et al. Dec 2013 A1
20130330637 Matsumoto et al. Dec 2013 A1
20130337189 Miller Dec 2013 A1
20130337304 Luski et al. Dec 2013 A1
20130337335 Kim et al. Dec 2013 A1
20130337338 Tikhonov et al. Dec 2013 A1
20130337339 Tikhonov et al. Dec 2013 A1
20130337340 Tikhonov et al. Dec 2013 A1
20130337341 Tikhonov et al. Dec 2013 A1
20130337343 Tokuda et al. Dec 2013 A1
20130337346 Miyoshi et al. Dec 2013 A1
20130344360 Miyajama et al. Dec 2013 A1
20130344383 Loveness et al. Dec 2013 A1
20130344390 Chen et al. Dec 2013 A1
20130344391 Yushin et al. Dec 2013 A1
20130344392 Huang et al. Dec 2013 A1
20130344396 Bosnyak et al. Dec 2013 A1
20130344397 Visco et al. Dec 2013 A1
20140011081 Ahn et al. Jan 2014 A1
20140011088 Lopatin et al. Jan 2014 A1
20140015160 Kung et al. Jan 2014 A1
20140017547 Eichinger Jan 2014 A1
20140017549 Miyazaki et al. Jan 2014 A1
20140017557 Lockett et al. Jan 2014 A1
20140017558 Lockett et al. Jan 2014 A1
20140017559 Kawasaki et al. Jan 2014 A1
20140017568 Gadkaree et al. Jan 2014 A1
20140017571 Lockett et al. Jan 2014 A1
20140017573 Otsuki et al. Jan 2014 A1
20140023884 Miller Jan 2014 A1
20140023932 Zhang et al. Jan 2014 A1
20140023934 Otsuki et al. Jan 2014 A1
20140027677 Lipka et al. Jan 2014 A1
20140030559 Yazami et al. Jan 2014 A1
20140030609 Abe et al. Jan 2014 A1
20140030610 Abe et al. Jan 2014 A1
20140030623 Chiang et al. Jan 2014 A1
20140038006 Sturm et al. Feb 2014 A1
20140038043 Hirayama et al. Feb 2014 A1
20140038059 Li et al. Feb 2014 A1
20140038060 Abe Feb 2014 A1
20140045015 Yokoyama et al. Feb 2014 A1
20140045016 Okutani et al. Feb 2014 A1
20140045017 Nonaka et al. Feb 2014 A1
20140045019 Yokoyama et al. Feb 2014 A1
20140045020 Okutani et al. Feb 2014 A1
20140045021 Okutani et al. Feb 2014 A1
20140045022 Matsuda et al. Feb 2014 A1
20140045065 Bao et al. Feb 2014 A1
20140045096 Berger et al. Feb 2014 A1
20140050910 Mukherjee et al. Feb 2014 A1
20140050972 Amiruddin et al. Feb 2014 A1
20140057153 Visco et al. Feb 2014 A1
20140057168 Newbound et al. Feb 2014 A1
20140057169 George et al. Feb 2014 A1
20140057172 Jeong et al. Feb 2014 A1
20140057173 Jeong et al. Feb 2014 A1
20140057179 Yushin et al. Feb 2014 A1
20140059820 Wright et al. Mar 2014 A1
20140060859 Kountz et al. Mar 2014 A1
20140065461 Kountz et al. Mar 2014 A1
20140065479 Yamada et al. Mar 2014 A1
20140072837 Sastry et al. Mar 2014 A1
20140072843 Liemersdorf et al. Mar 2014 A1
20140072871 Chen et al. Mar 2014 A1
20140072877 Araki et al. Mar 2014 A1
20140072879 Chen et al. Mar 2014 A1
20140075745 Lu et al. Mar 2014 A1
20140080012 Minami et al. Mar 2014 A1
20140087214 Amatucci et al. Mar 2014 A1
20140087250 Coowar et al. Mar 2014 A1
20140087251 Takahashi et al. Mar 2014 A1
20140087257 Gopukumar et al. Mar 2014 A1
20140093780 Tabuchi et al. Apr 2014 A1
20140093783 Lamanna et al. Apr 2014 A1
20140093787 Abe et al. Apr 2014 A1
20140099528 Lockett et al. Apr 2014 A1
20140099539 Yamazaki et al. Apr 2014 A1
20140099557 Doe et al. Apr 2014 A1
20140099560 Parans Paranthaman et al. Apr 2014 A1
20140102884 Miller Apr 2014 A1
20140104754 Lipka et al. Apr 2014 A1
20140106219 Wang et al. Apr 2014 A1
20140107326 Swager et al. Apr 2014 A1
20140113202 Sun et al. Apr 2014 A1
20140113203 Xiao et al. Apr 2014 A1
20140117940 Takahata May 2014 A1
20140125292 Best et al. May 2014 A1
20140127567 Kuriki et al. May 2014 A1
20140127575 Scrosati et al. May 2014 A1
20140131217 Buschmann May 2014 A1
20140132220 Jamison May 2014 A1
20140134499 Newbound et al. May 2014 A1
20140134501 Li et al. May 2014 A1
20140134521 Naito et al. May 2014 A1
20140138591 Yoon et al. May 2014 A1
20140140912 Ivanovic-Burmazovic et al. May 2014 A1
20140141336 Morin May 2014 A1
20140141337 Morin May 2014 A1
20140141340 Egorov et al. May 2014 A1
20140146440 Gadkaree et al. May 2014 A1
20140147710 Schaefer May 2014 A1
20140147741 Shin et al. May 2014 A1
20140147752 Pratt et al. May 2014 A1
20140154546 Carter et al. Jun 2014 A1
20140154557 Mori et al. Jun 2014 A1
20140154559 Mori et al. Jun 2014 A1
20140154587 Abe et al. Jun 2014 A1
20140154590 Kramer et al. Jun 2014 A1
20140162108 Visco et al. Jun 2014 A1
20140162130 Barsoum et al. Jun 2014 A1
20140162131 Friend et al. Jun 2014 A1
20140162135 Prieto et al. Jun 2014 A1
20140166929 Takeuchi et al. Jun 2014 A1
20140166939 Park et al. Jun 2014 A1
20140170303 Rayner et al. Jun 2014 A1
20140170465 Visco et al. Jun 2014 A1
20140170475 Park et al. Jun 2014 A1
20140170480 Oladeji Jun 2014 A1
20140170482 Park et al. Jun 2014 A1
20140170498 Park Jun 2014 A1
20140170500 Oguni et al. Jun 2014 A1
20140170503 Yushin et al. Jun 2014 A1
20140170524 Chiang et al. Jun 2014 A1
20140173300 Yamazaki et al. Jun 2014 A1
20140176074 Kako et al. Jun 2014 A1
20140176076 Momo et al. Jun 2014 A1
20140178759 Worsley et al. Jun 2014 A1
20140178770 Xu et al. Jun 2014 A1
20140178772 Jeong et al. Jun 2014 A1
20140184162 Takahashi et al. Jul 2014 A1
20140184172 Momo et al. Jul 2014 A1
20140193712 Yushin et al. Jul 2014 A1
20140196631 McDaniel Jul 2014 A1
20140197797 Yamazaki Jul 2014 A1
20140197801 Nuzzo et al. Jul 2014 A1
20140197802 Yamazaki Jul 2014 A1
20140197805 Greening et al. Jul 2014 A1
20140199585 Rupert et al. Jul 2014 A1
20140199599 Yu et al. Jul 2014 A1
20140199600 Yawata et al. Jul 2014 A1
20140199613 Chappey et al. Jul 2014 A1
20140205905 Xiao et al. Jul 2014 A1
20140205908 Wohrle et al. Jul 2014 A1
20140212716 Farmer et al. Jul 2014 A1
20140212752 Arakawa et al. Jul 2014 A1
20140212761 Kitagawa et al. Jul 2014 A1
20140212763 Tzeng et al. Jul 2014 A1
20140212770 Abe et al. Jul 2014 A1
20140220417 Cheng et al. Aug 2014 A1
20140220422 Rogers et al. Aug 2014 A1
20140220450 Jilek et al. Aug 2014 A1
20140225569 Yamazaki et al. Aug 2014 A1
20140227432 Liu et al. Aug 2014 A1
20140227548 Myrick Aug 2014 A1
20140227584 Holstein et al. Aug 2014 A1
20140230887 Eguchi et al. Aug 2014 A1
20140234693 Tsujikawa et al. Aug 2014 A1
20140234705 Yayamoto et al. Aug 2014 A1
20140234711 Rojeski Aug 2014 A1
20140234712 Rojeski Aug 2014 A1
20140234713 Rojeski Aug 2014 A1
20140234726 Christensen et al. Aug 2014 A1
20140234727 Abe et al. Aug 2014 A1
20140234732 Park et al. Aug 2014 A1
20140239905 Yamazaki Aug 2014 A1
20140242445 Gozdz et al. Aug 2014 A1
20140242453 Lee et al. Aug 2014 A1
20140242469 Yamamoto et al. Aug 2014 A1
20140242474 Matsui et al. Aug 2014 A1
20140245599 Voelker et al. Sep 2014 A1
20140246905 Yamazaki et al. Sep 2014 A1
20140248521 Chiang et al. Sep 2014 A1
20140248526 Wohrle et al. Sep 2014 A1
20140248537 Hayashi et al. Sep 2014 A1
20140255792 Cao et al. Sep 2014 A1
20140255802 Barde et al. Sep 2014 A1
20140256534 Gao et al. Sep 2014 A1
20140264198 Tong et al. Sep 2014 A1
20140266075 Gellett et al. Sep 2014 A1
20140272132 Frianeza-Kullberg Sep 2014 A1
20140272489 Anandan et al. Sep 2014 A1
20140272524 Visco et al. Sep 2014 A1
20140272531 Manning Sep 2014 A1
20140272553 Cheng et al. Sep 2014 A1
20140272558 Xiao et al. Sep 2014 A1
20140272567 Zhang et al. Sep 2014 A1
20140272568 Frianeza-Kullberg Sep 2014 A1
20140272574 Son et al. Sep 2014 A1
20140272576 Kamat et al. Sep 2014 A1
20140272577 Hartner et al. Sep 2014 A1
20140272578 Xiao et al. Sep 2014 A1
20140272579 Frianeza-Kullberg Sep 2014 A1
20140272580 Frianeza-Kullburg Sep 2014 A1
20140272583 Hellring et al. Sep 2014 A1
20140272591 Vanier et al. Sep 2014 A1
20140287301 Yushin et al. Sep 2014 A1
20140287305 Wachsman et al. Sep 2014 A1
20140287323 Lu et al. Sep 2014 A1
20140287325 Abe et al. Sep 2014 A1
20140287330 Ohlsen Sep 2014 A1
20140293507 Gadkaree et al. Oct 2014 A1
20140295268 Wang et al. Oct 2014 A1
20140295270 Adachi et al. Oct 2014 A1
20140295275 Kay Oct 2014 A1
20140295290 Park et al. Oct 2014 A1
20140302354 Shao et al. Oct 2014 A1
20140302373 Lockett et al. Oct 2014 A1
20140302400 Shao et al. Oct 2014 A1
20140302401 Burkhardt et al. Oct 2014 A1
20140302402 Chen et al. Oct 2014 A1
20140302403 Doe et al. Oct 2014 A1
20140306162 Poe et al. Oct 2014 A1
20140308562 Jeong et al. Oct 2014 A1
20140308583 Manthiram et al. Oct 2014 A1
20140308585 Han et al. Oct 2014 A1
20140308588 Hirakawa et al. Oct 2014 A1
20140310951 Grant et al. Oct 2014 A1
20140312269 Laumann et al. Oct 2014 A1
20140314948 Braun et al. Oct 2014 A1
20140315072 Kobayashi et al. Oct 2014 A1
20140315091 Yamazaki et al. Oct 2014 A1
20140315097 Tan et al. Oct 2014 A1
20140315104 Liu et al. Oct 2014 A1
20140319649 Forster et al. Oct 2014 A1
20140322579 Mitsuhashi et al. Oct 2014 A1
20140322602 Yamazaki et al. Oct 2014 A1
20140322608 Claussen et al. Oct 2014 A1
20140329120 Cui et al. Nov 2014 A1
20140329131 Jo et al. Nov 2014 A1
20140329150 de Guzman et al. Nov 2014 A1
20140332715 Kawakami et al. Nov 2014 A1
20140335406 An Nov 2014 A1
20140335410 Loveridge et al. Nov 2014 A1
20140335411 Liu et al. Nov 2014 A1
20140342200 Morita et al. Nov 2014 A1
20140342209 He et al. Nov 2014 A1
20140342223 Voelker et al. Nov 2014 A1
20140342228 Liu et al. Nov 2014 A1
20140342240 Harrup et al. Nov 2014 A1
20140342244 West et al. Nov 2014 A1
20140342249 He et al. Nov 2014 A1
20140346618 Lahlouh et al. Nov 2014 A1
20140349182 O'Neill et al. Nov 2014 A1
20140349186 Burton et al. Nov 2014 A1
20140353146 Gilliam et al. Dec 2014 A1
20140356703 Dennes et al. Dec 2014 A1
20140356708 Arikawa et al. Dec 2014 A1
20140356735 Pena Hueso et al. Dec 2014 A1
20140363735 Yoshida et al. Dec 2014 A1
20140363746 He et al. Dec 2014 A1
20140370379 Inoue et al. Dec 2014 A1
20140370380 Cui et al. Dec 2014 A9
20140370387 Anguchamy et al. Dec 2014 A1
20140370396 Kang et al. Dec 2014 A1
20140376160 Kako et al. Dec 2014 A1
20140377635 Matsumoto et al. Dec 2014 A1
20140377648 Gennett et al. Dec 2014 A1
20140377667 Roschenthaler et al. Dec 2014 A1
20140377668 Abe et al. Dec 2014 A1
20150002162 Rich et al. Jan 2015 A1
20150004444 Christensen et al. Jan 2015 A1
20150004480 Gardner et al. Jan 2015 A1
20150004482 Gardner et al. Jan 2015 A1
20150004488 Abdelsalam et al. Jan 2015 A1
20150004495 Cui et al. Jan 2015 A1
20150010460 Takeuchi et al. Jan 2015 A1
20150010784 Takahata et al. Jan 2015 A1
20150014184 Swonger Jan 2015 A1
20150014581 Kawakami et al. Jan 2015 A1
20150014605 Kawakami et al. Jan 2015 A1
20150017541 Tajima et al. Jan 2015 A1
20150017543 Lee et al. Jan 2015 A1
20150017544 Prasad et al. Jan 2015 A1
20150017549 Nishimura et al. Jan 2015 A1
20150017550 Nishimura et al. Jan 2015 A1
20150022957 Hiroki et al. Jan 2015 A1
20150024121 He et al. Jan 2015 A1
20150024248 He et al. Jan 2015 A1
20150024249 Lim et al. Jan 2015 A1
20150024251 Visco et al. Jan 2015 A1
20150024279 Tan et al. Jan 2015 A1
20150030856 Singh et al. Jan 2015 A1
20150030906 Amin-Sanayei et al. Jan 2015 A1
20150030939 Amereller et al. Jan 2015 A1
20150037675 Izuhara et al. Feb 2015 A1
20150037686 Pena Hueso et al. Feb 2015 A1
20150037689 Nishimura et al. Feb 2015 A1
20150037690 Dalavi et al. Feb 2015 A1
20150044517 Mikhaylik et al. Feb 2015 A1
20150044533 Rode et al. Feb 2015 A1
20150044556 Wang et al. Feb 2015 A1
20150044564 Wang et al. Feb 2015 A1
20150044565 Wang et al. Feb 2015 A1
20150044571 Abdelsalam et al. Feb 2015 A1
20150044573 Roschenthaler et al. Feb 2015 A1
20150044581 Holme et al. Feb 2015 A1
20150050535 Amiruddin et al. Feb 2015 A1
20150050564 Mizuno et al. Feb 2015 A1
20150050565 Lamanna et al. Feb 2015 A1
20150056488 Zhang et al. Feb 2015 A1
20150056499 Dai et al. Feb 2015 A1
20150056507 Dadheech et al. Feb 2015 A1
20150056509 Jeong et al. Feb 2015 A1
20150056514 Dai et al. Feb 2015 A1
20150056516 Hellring et al. Feb 2015 A1
20150056521 Burns et al. Feb 2015 A1
20150062687 Milliron et al. Mar 2015 A1
20150064514 Wu et al. Mar 2015 A1
20150064538 Bosnyak et al. Mar 2015 A1
20150064568 Yushin et al. Mar 2015 A1
20150064574 He et al. Mar 2015 A1
20150064575 He et al. Mar 2015 A1
20150064578 Kang et al. Mar 2015 A1
20150064580 Bridges et al. Mar 2015 A1
20150069307 Parans Paranthaman et al. Mar 2015 A1
20150072225 Ishiji et al. Mar 2015 A1
20150072232 Nagai Mar 2015 A1
20150072234 Mitchell et al. Mar 2015 A1
20150072247 Cho et al. Mar 2015 A1
20150073632 Hill Mar 2015 A1
20150079477 Spahr et al. Mar 2015 A1
20150079483 Cresce et al. Mar 2015 A1
20150079484 Cresce et al. Mar 2015 A1
20150086859 Chang et al. Mar 2015 A1
20150086865 Oda Mar 2015 A1
20150086868 Inoue et al. Mar 2015 A1
20150086876 Taeda et al. Mar 2015 A1
20150086877 Yamazaki et al. Mar 2015 A1
20150089797 Binder et al. Apr 2015 A1
20150093459 Mora-Gutierrez et al. Apr 2015 A1
20150093631 Kawasaki et al. Apr 2015 A1
20150093647 Kako et al. Apr 2015 A1
20150093653 Coowar et al. Apr 2015 A1
20150093654 Galiano et al. Apr 2015 A1
20150093655 Kozelj et al. Apr 2015 A1
20150093659 Gonzalez et al. Apr 2015 A1
20150099165 Dippel et al. Apr 2015 A1
20150099171 Alarco et al. Apr 2015 A1
20150099178 Kawakami et al. Apr 2015 A1
20150099179 Ikenuma et al. Apr 2015 A1
20150099184 Rojeski et al. Apr 2015 A1
20150099185 Joo et al. Apr 2015 A1
20150099187 Cui et al. Apr 2015 A1
20150099188 Holme et al. Apr 2015 A1
20150099190 Holme et al. Apr 2015 A1
20150099191 Liu et al. Apr 2015 A1
20150099192 Yawata et al. Apr 2015 A1
20150102257 Mullins et al. Apr 2015 A1
20150104701 Azami Apr 2015 A1
20150104712 Kerlau et al. Apr 2015 A1
20150104716 Kang et al. Apr 2015 A1
20150110971 Oladeji Apr 2015 A1
20150111078 Hosoya et al. Apr 2015 A1
20150111086 Arnold et al. Apr 2015 A1
20150111088 Hiroki et al. Apr 2015 A1
20150111099 Zhang Apr 2015 A1
20150111101 Ikenuma et al. Apr 2015 A1
20150111107 Oguni et al. Apr 2015 A1
20150118558 Yamazaki et al. Apr 2015 A1
20150118565 Bell et al. Apr 2015 A1
20150118572 Lund et al. Apr 2015 A1
20150118588 McLean et al. Apr 2015 A1
20150125595 Lahlouh et al. May 2015 A1
20150125752 Nishimura et al. May 2015 A1
20150125759 Xu et al. May 2015 A1
20150125761 Shimamoto et al. May 2015 A1
20150131047 Saylor et al. May 2015 A1
20150132648 Inoue et al. May 2015 A1
20150132649 Ogino et al. May 2015 A1
20150137030 Matsuo et al. May 2015 A1
20150140206 O'Neill et al. May 2015 A1
20150140397 Tajima et al. May 2015 A1
20150140398 Yamazaki May 2015 A1
20150140427 Zhang et al. May 2015 A1
20150140434 Jung May 2015 A1
20150140446 Li May 2015 A1
20150140449 Ishikawa et al. May 2015 A1
20150143806 Friesth May 2015 A1
20150147602 Bianchi et al. May 2015 A1
20150147624 Yamafuku et al. May 2015 A1
20150147642 Ling et al. May 2015 A1
20150147645 Lee et al. May 2015 A1
20150147662 Park et al. May 2015 A1
20150152566 Zhang et al. Jun 2015 A1
20150155546 Yushin et al. Jun 2015 A1
20150155556 Kawakami et al. Jun 2015 A1
20150155557 Kwon et al. Jun 2015 A1
20150155559 Zimmerman et al. Jun 2015 A1
20150155598 Yazami Jun 2015 A1
20150162131 Felten et al. Jun 2015 A1
20150162139 Lin et al. Jun 2015 A1
20150162588 Lee et al. Jun 2015 A1
20150162602 Dadheech et al. Jun 2015 A1
20150162603 Yushin et al. Jun 2015 A1
20150162772 Peterson et al. Jun 2015 A1
20150171414 Takahata et al. Jun 2015 A1
20150171426 Wang et al. Jun 2015 A1
20150171467 Dubois et al. Jun 2015 A1
20150179976 Galand et al. Jun 2015 A1
20150180001 Johnson et al. Jun 2015 A1
20150180023 Xiao et al. Jun 2015 A1
20150180087 Kim et al. Jun 2015 A1
20150180249 Jeon et al. Jun 2015 A1
20150188125 Korgel et al. Jul 2015 A1
20150188187 Strand et al. Jul 2015 A1
20150188189 Armand et al. Jul 2015 A1
20150188191 Kalinovich et al. Jul 2015 A1
20150191423 Bomkamp et al. Jul 2015 A1
20150191607 McDaniel Jul 2015 A1
20150191841 Grant et al. Jul 2015 A1
20150194702 Tokunaga et al. Jul 2015 A1
20150200390 Lu et al. Jul 2015 A1
20150200420 Holme et al. Jul 2015 A1
20150200422 Lee et al. Jul 2015 A1
20150203516 Zhang et al. Jul 2015 A1
20150207147 Nagai et al. Jul 2015 A1
20150207174 Lee et al. Jul 2015 A1
20150207176 Moganty et al. Jul 2015 A1
20150207184 Kunze et al. Jul 2015 A1
20150210044 Barsoum et al. Jul 2015 A1
20150214529 Yawata et al. Jul 2015 A1
20150214573 Sastry et al. Jul 2015 A1
20150214577 O'Neill et al. Jul 2015 A1
20150221936 Huang Aug 2015 A1
20150221983 Kamiya et al. Aug 2015 A1
20150221987 Yawata et al. Aug 2015 A1
20150228980 Huang Aug 2015 A1
20150236343 Xiao et al. Aug 2015 A1
20150236372 Yushin et al. Aug 2015 A1
20150236378 Kuwajima et al. Aug 2015 A1
20150236379 Wietelmann et al. Aug 2015 A1
20150236380 Garsuch et al. Aug 2015 A1
20150243936 Miyagi et al. Aug 2015 A1
20150243962 Hiroki et al. Aug 2015 A1
20150243972 Ito et al. Aug 2015 A1
20150243973 Newbound et al. Aug 2015 A1
20150243987 Lu et al. Aug 2015 A1
20150243988 Lu et al. Aug 2015 A1
20150244041 Sastry et al. Aug 2015 A1
20150248149 Yamazaki et al. Sep 2015 A1
20150249247 Zhou et al. Sep 2015 A1
20150249262 Wachsman et al. Sep 2015 A1
20150255771 Yu Sep 2015 A1
20150261254 Hiroki et al. Sep 2015 A1
20150262761 Gadkaree et al. Sep 2015 A1
20150263342 Newbound et al. Sep 2015 A1
20150263379 Xiao et al. Sep 2015 A1
20150263543 Gellett et al. Sep 2015 A1
20150270552 Lee et al. Sep 2015 A1
20150270573 Pena Hueso et al. Sep 2015 A1
20150280218 Zimmerman et al. Oct 2015 A1
20150280219 Xiao et al. Oct 2015 A1
20150280229 Chen et al. Oct 2015 A1
20150280239 Hellring et al. Oct 2015 A1
20150280267 Chiang et al. Oct 2015 A1
20150280281 Farmer Oct 2015 A1
20150288028 DeSimone et al. Oct 2015 A1
20150288031 Zhang et al. Oct 2015 A1
20150295241 Liang et al. Oct 2015 A1
20150295275 Han et al. Oct 2015 A1
20150295276 Ishiji Oct 2015 A1
20150299852 Ozkan et al. Oct 2015 A1
20150303481 Duong et al. Oct 2015 A1
20150311509 Ando et al. Oct 2015 A1
20150311525 Masarapu et al. Oct 2015 A1
20150311564 Ishiji Oct 2015 A1
20150318530 Yushin et al. Nov 2015 A1
20150318543 Lee et al. Nov 2015 A1
20150318555 Oku et al. Nov 2015 A1
20150318570 Choi et al. Nov 2015 A1
20150318572 Kuwajima et al. Nov 2015 A1
20150318578 Abe et al. Nov 2015 A1
20150318580 Fukunaga et al. Nov 2015 A1
20150321920 Geramita et al. Nov 2015 A1
20150325831 Dennes et al. Nov 2015 A1
20150325843 Yoon et al. Nov 2015 A1
20150325852 Wang et al. Nov 2015 A1
20150325856 Federici et al. Nov 2015 A1
20150325880 Kim et al. Nov 2015 A1
20150325882 Yushin et al. Nov 2015 A1
20150325884 Fukunaga et al. Nov 2015 A1
20150333310 Choi et al. Nov 2015 A1
20150333315 Yoon et al. Nov 2015 A1
20150333332 Wietelmann et al. Nov 2015 A1
20150333359 Takahashi et al. Nov 2015 A1
20150333360 Tajima et al. Nov 2015 A1
20150333370 Abe et al. Nov 2015 A1
20150333371 Chen et al. Nov 2015 A1
20150337443 Albrecht et al. Nov 2015 A1
20150340679 Shimura et al. Nov 2015 A1
20150340738 Moganty et al. Nov 2015 A1
20150340739 Klaehn et al. Nov 2015 A1
20150349338 Zhao et al. Dec 2015 A1
20150349375 Takahashi et al. Dec 2015 A1
20150349376 Shin et al. Dec 2015 A1
20150357125 Lockett et al. Dec 2015 A1
20150357126 Lockett et al. Dec 2015 A1
20150357646 Lu et al. Dec 2015 A1
20150357677 Lockett et al. Dec 2015 A1
20150361564 Albrecht et al. Dec 2015 A1
20150364739 Stacy et al. Dec 2015 A1
20150364747 Elam et al. Dec 2015 A1
20150364748 Amiruddin et al. Dec 2015 A1
20150364755 Liu et al. Dec 2015 A1
20150364791 Vu et al. Dec 2015 A1
20150364794 Nakazawa et al. Dec 2015 A1
20150364795 Stefan et al. Dec 2015 A1
20150364796 Li et al. Dec 2015 A1
20150372296 Jones et al. Dec 2015 A1
20150372305 Matsuo et al. Dec 2015 A1
20150372346 Sastry et al. Dec 2015 A1
20150372349 Shikita Dec 2015 A1
20150373831 Rogers et al. Dec 2015 A1
20150377977 Yazami et al. Dec 2015 A1
20150380355 Rogers et al. Dec 2015 A1
20150380727 Hao et al. Dec 2015 A1
20150380728 Son et al. Dec 2015 A1
20150380731 Tong et al. Dec 2015 A1
20150380772 Tokuda et al. Dec 2015 A1
20150380777 Takahashi et al. Dec 2015 A1
Foreign Referenced Citations (3)
Number Date Country
H11-80395 Mar 1999 JP
2005117199 Dec 2005 WO
2014185959 Nov 2014 WO
Non-Patent Literature Citations (13)
Entry
International Search Report for PCT/US206/024515 dated Jul. 19, 2016.
Written Opinion for PCT/US2016/024515 dated Jul. 19, 2016.
—ao, Xia, et al_ “Novel phosphamide additive to improve thermal stability of solid electrolyte interphase on graphite anode in lithium-ion batteries.” Acs applied materials & interfaces 5.22 (2013): 11494-11497.
Nelson, Jeffrey T., and Carla F Green_ Organic electrolyte battery systems. No_ Hdl-Tr-1588_ Harry Diamond _ABS Adelphi Md, 1972.
-larrup, Mason K., et al_ “Phosphazene Based Additives for Improvement of Safety and Battery Lifetimes in Lithium-Ion 3atteries.” Ecs Transactions 41.39 (2012): 13-25.
Gering, Kevin L., et al. Section Iv. D. 3 for Doe 2013 Annual Report: Novel Phosphazene-Based Compounds to Enhance Safety and Stability of Cell Chemistries for High Voltage Applications (Inl). No. Inl/Ext-13-30529. Idaho National Laboratory (Inl), 2013.
3ieker, Georg, Martin Winter, and Peter Bieker. “Electrochemical in situ investigations of Sei and dendrite formation o he lithium metal anode.” Physical Chemistry Chemical Physics 17.14 (2015): 8670-8679.
Song, J. Y., Y. Y. Wang, and C_ C. Wan_ “Review of gel-type polymer electrolytes for lithium-ion batteries.” Journal of Sower Sources 77.2 (1999): 183-197.
Doyle, Marc, Thomas F Fuller, and John Newman. “Modeling of galvanostatic charge and discharge of the lithium/ 3olymer/insertion cell.” Journal of the Electrochemical Society 140.6 (1993): 1526-1533.
Rollins, Harry W., et al. “Fluorinated phosphazene co-solvents for improved thermal and safety performance in lithium-on battery electrolytes.” Journal of Power Sources 263 (2014): 66-74.
Richardson, Rebekah Made. “New synthesis and reactions of phosphonates.” (2012).
Ku, Kang, et al. “An attempt to formulate nonflammable lithium ion electrolytes with alkyl phosphates and phosphazenes.” Journal of the Electrochemical Society 149.5 (2002): A622-A626_.
Mang, Sheng Shui. “A review on electrolyte additives for lithium-ion batteries.” Journal of Power Sources 162.2 2006): 1379-1394.
Related Publications (1)
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20160285125 A1 Sep 2016 US
Provisional Applications (1)
Number Date Country
62139552 Mar 2015 US