Patent Application
20180111108
This application claims priority from European Patent Application No. 11195377.4 filed Dec. 22, 2011 and European Patent Application No. 12157429.7 filed Feb. 29, 2012, the entire disclosure of which is incorporated herein by reference.
The present invention concerns conductive microparticles suitable for being used in electrodes of lithium ion batteries as well as methods for the production of such miroparticles and electrodes.
The electroactive materials of electrodes of lithium ion batteries comprise at least one transition metal providing exchangeable valence electrons, said material also allowing insertion and removal or intercalation and deintercalation, respectively, of alkaline metal ions in order to keep neutrality of the material in case of exchange of valence electrons.
Some very interesting electroactive materials are not or not suficiently conductive per se. Such materials are used in the form of microparticles (also termed microparticulate form) or nanoparticles (also termed nanoparticulate form) and in combination with a conductive matrix. Additional improvement is obtained if the particles are conductively coated.
It is assumed that conductive coatings add to the structural integrity of the particels because of improved regularity of electric field distribution on the surface of the particles and therewith connected improved structural integrity. In addition, even if the electroactive material particles are partially disintegrated over an extended number of cycles, the carbon coating proved advantageous. This may be due to encapsulation of the disintegrated particles and—if breaking apart—in partially conductively coated fragments. Methods for providing microparticles with a conductive coating are known. The preferred coating is a coating with carbonaceous material.
Carbon and carbonaceous materials are known as good electrical conductors and are already used to increase the electronic conductivity of electroactive materials. In general, carbon coating of oxide materials is carried out using a pyrolysis process that forms a thin layer of carbonaceous material such as pyrolitic graphite on the surface of particles provided that the electroactive core material is sufficiently stable in reducing atmosphere (see U.S. Pat. No. 6,962,266). According to U.S. Pat. No. 6,962,266, the carbonaceous coating may be obtained through thermal decomposition or through dehydrogenation, e.g. by partial oxidation of organic materials such as hydrocarbons and their derivatives like polycyclic aromatic moieties, sugars, carbon hydride and polymers. In some embodiments a lithium salt of carboxylic acids is used for simultaneous lithiation and pyrolytic carbonatious coating formation.
However, the problem with the coatings of the state of the art is that the pyrolysis reaction is not well defined. During pyrolysis, the hydrocarbon or carboxylic acid deposits may release compounds in different stats of oxidation/reduction like hydrogen or water and carbon oxides or dioxides resulting in an inhomogeneous coating of not clearly defined composition and possibly in affected EAMs.
Thus, there is still a need for high energy storage materials with a good conductive coating and a method for obtaining such materials preferably in a one step reaction.
Hence, it is a general object of the invention to provide optimized coating methods and therewith obtainable optimized carbon coated electroactive particles with a coating having improved homogeneity and purity.
Now, in order to implement these and still further objects of the invention, which will become more readily apparent as the description proceeds, the method for producing conductively coated particles comprising an at least partially metallated electroactive core material is manifested by comprising the steps of premixing an oxidant electroactive material with a metallated reductant followed by chemically reacting the oxidant electroactive material with the metallated reductant, said reductant being a coating precursor, said metal being at least one alkaline and/or at least one alkaline earth metal, and said chemically reacting being performed under conditions allowing reduction and metallation of the electroactive material via insertion/intercalation of the alkalinemetal cation(s) and/or the alkaline earth metal cation(s) and coating formation via a polymerisation reaction, like polyanionic or radicalic polymerisation, of the reductant.
The terms insertion and intercalation or deinsertion and deintercalation, respectively are used interchangeably for both crystalline and amorphous materials.
A metal comprising compound is termed metallated.
Insertion or intercalation, respectively, of different alkaline and/or alkaline earth metals at the same time like Li and Na and/or K can lead to a more stable system. Thus the use of mixed metallated reductants like Li2-xNaxC2 (x≤1) and/or Li2-xKxC2 (x≤1) is also of interest.
In one embodiment, the metallated reductant comprises or consists of alkaline metal(s), wherein the alkaline metal(s) comprises at least 50% lithium, preferably at least 95% lithium, more preferred at least 99% lithium.
For sake of readability, in the following description lithium is mentioned although besides of lithium sodium and potassium may also be present, or alkaline earth metals alone or in combination with alkaline metals.
The method of the present invention is a one step method that allows simultaneous lithiation and coating of inorganic oxidants. The coating is not limited to carbon although carbon is preferred but may e.g. also be a boron nitride or a carbon nitride coating. Other possible coatings comprise CBx from B═C═B4− compounds like Li4CB2, CBxNy from a lithium pyrazine precursor like Ca10-xLi2x(BN2)4(CBN)2 (see also WO 2004/069768), (SyN)x from e.g. LigNS3, (CH)x (polyacetylene) for example form LiHC2.
The conditions allowing reduction and lithiation comprise applying energy in the form of
In preferred embodiments, the chemical reaction can be induced either via thermal treatment of via tribological treatment, e.g. by ball milling.
Both methods lead to conductively coated particles comprising an at least partially lithiated electroactive core material, but to different core materials. While heat treatment produces a crystalline at least partially lithiated electroactive core material, ball milling results in an almost amorphous at least partially lithiated electroactive core material. This difference in the at least partially lithiated electroactive core material, i.e. whether it is crystalline or amorphous, has a strong influence on the electrochemical behavior.
The reaction is a redox reaction of the form
M
xreductant+oxidant→Mxoxidantreduced+reductantsurface(reductantoxidized)
In the following description, the electroactive material or electroactive core material or oxidant is abbreviated as EAM and the at least partially lithiated electroactive core material as LiEAM.
Different to pyrolysis, the carbon coating takes place via a stoichiometric reaction according to the equation 1:
x Li2C2 +Oxidant Li2xOxidantreduced+2x Csurface
Boron nitride coating and lithiation of formally inorganic oxidants may be obtained by reaction with Li3BN2 according to the following equation 2:
x Li3BN2+Oxidant Li3xOxidantreduced+x BNsurface x/2 N2
Carbon nitride coating and lithiation of formally inorganic oxidants may be obtained by reaction with Li2CN2 according to the following equation 3:
x Li2CN2+Oxid ant Li2xOxidantreduced+x CN2x-y surface y/2 N2
Possible Oxidants are:
The EAMs preferably are in the form of microparticles or even nanoparticles. Usually they have average diameters below 10 μm, preferably below 5 μm, more preferred below 1 μm and especially below 500 nm, in particular they are nanoparticles having an average particle size in the range of 5 to 500 nm, preferably in the range of 5 to 400 nm, more preferred in the range of 20 to 300 nm.
Also the lithium providing reductants are preferably of small size. For example lithium carbide (Li2C2) after synthesis has a particle size of 10 to 100 μm. Since an as small as possible particle size is assumed to improve homogeneity of the coating, it is reduced in size, e.g. by ball milling for 1 hour with 500 rpm, to end up with a homogeneous particle size of 1-5 μm.
Particle sizes of <10 μm, preferably 100 nm to 5 μm, more preferred 0.5 to 1.5 μm are generally preferred for all Li and coating providing reductants.
Although (as shown above) other than carbon coatings can be applied via the inventive methods, carbon is presently preferred due to its conductivity that is better than the one of CN and BN and because of the good availability of suitable metallated precursors.
The invention is now further described for a carbon coating. However, the respective information is also applicable to other coatings.
Due to the stoichiometry of the reactions, the thickness of the coating can only be varied by variation of the particle size of the EAM or—for thinner coatings—by starting from an EAM that has already been partially lithiated. For a carbon coating starting from Li2C2, the amount of surface carbon corresponds to the amount of lithium taken up by the EAM. Since big particles have a higher ratio between volume and surface, as a rule the coating will be much thicker for big particles. The minimal thickness of 2 nm so far was observed for a 40 nm particle of LiFePO4 and a maximum thickness of 30 nm for a 5 μm large particle of LiV2O5. It was found that even the thick coating of 30 nm allows intercalation/deintercalation, although at somewhat lower speed than a thin coating. The minimal thickness of a coating is assumed to be below 1 nm but presumably above 0.5 nm because the product deposited is not graphene. In addition, it is also assumed that the coating is protecting the EAM and therewith enhancing the cycle stability. Thus, the average thickness of the coating is preferably between 0.5 to 30 nm, more preferred between 0.5 to 2 nm.
Theoretically, the ideal thickness of the carbon coating is just thick enough to
In any case, it was found that in most cases partial or complete intercalation of cathode materials during this process improves their electrochemical properties.
In view of the homogeneous coverage of the particles with the carbon, some migration of the carbon on the surface of the particles is assumed.
Irrespective of whether the reaction is performed by ball milling or heat treatment, the reactants preferably are carefully premixed, in order to ensure that the reaction is started with homogeneously mixed starting materials.
The whole reaction, also the premixing can and preferably is performed in the absence of any solvent thereby avoiding any solvent removal step.
In e.g. the ball milling procedure the reaction starts directly. Suitable reaction conditions for this tribochemical step are e.g. a rotation speed of 200-1500 rpm during 15 to 45 minutes, such as around 30 minutes or 30 minutes. Hitherto optimal products were obtained with 400 rpm during 30 minutes. Also important is the ratio between the weight of the balls and the weight of the sample which with the presently used equipment was found to be in the range from 6:1 to 4:1, preferably around 5:1 like 5.2:1 to 4.8:1.
With the exception of the weight ratio the material of the balls is irrelevant, provided that it is sufficiently hard. Examples of suitable materials are: Agate, a modification of silica, steal, Cr2O3, and Al2O3
Since the reaction is only slightly exothermic, no raise of the overall temperature is observed during ball milling such that the tribochemical reaction is devoid of a thermal treatment.
The ball milling method therefore is also applicable for heat sensitive materials as H2V3O8 without risking decomposition.
The disadvantage of the ballmilling method is that the conditions are more difficult to adjust and that therefore it is more difficult to avoid side reactions (see below).
The ball milling method results in an amorphous material.
Heat treatment can be performed with fast heating rate of for example between 150 to 200 K/h like 180 K/h. In preferred embodiments, heat treatment is performed either with a slow heating rate or with high heating rate for an initial phase followed by a slow heating rate. A slow heating rate of e.g. between 50 to 70 K/h should be applied for about at least the last hour, i.e. starting at 50 to 70 K below the reaction temperature.
A presently preferred heating rate is around 60 K/h starting at about 60 K before reaching the reaction temperature. The fast heating rate for example may be between 150 to 200 K/h such as 180 K/h.
The reaction temperature depends on the EAM and can easily be determined by thermogravimetry at a heating rate of e.g. 10 K/min.
The advantage of the heat treatment are the very precisely adjustable conditions so that side reactions can be avoided.
The heat treatment leads to crystalline coated LiEAMs.
Since Li2C2 is a strong reductant care has to be taken that an intercalation takes place and not a reduction. As already indicated above, undesired side reactions have to be avoided by careful control of the reaction conditions. Such an undesired side reaction is e.g. shown in equation 4:
2 MnO2+Li2C22 MnO+Li2O2+C
From the coated particulate materials described herein electrodes can be prepared by mixing the coated LiEAM with an optionally electronically conducting binder, optionally in particulate form and optionally in the presence of conductive additives like conductive carbon. The binding of the particulate coated LiEAM can be performed in a solvent followed by drying.
Suitable binders are polyvinylidene fluoride (PVDF), poly(3,4-ethylenedioxythiophene) (PEDOT),1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide metho-p-toluenesulfonate or 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide methyl-p-toluenesulfonate (CMC), polytetrafluoroethylene (PTFE), fluoro polymer rubber (FKS), styrene-butadiene rubber (SBR), polyacrylnitrile(PAN), polyurethane, polyacrylic acid, polyamide, polyacrylate, and polyvinylether.
Suitable conductive carbons are SuperP® or Super P Li® Carbon (obtainable from TIMCAL) or nanofibers or nanotubes.
Suitable solvents are a mixture of aprotic polar and aprotic apolar solvents like THF/Toluene 4:1.
Dependent on the thermostability drying is preferably either performed at temperatures well above 100° C. like 180° C. under air, or at temperatures below 100° C. like 80° C. under vacuum.
Such electrodes can be used together with any suitable anode, and an electrolyte like LiPF6 or Li(C2F5)3PF3 (e.g. 1M in ethylene carbonate : dimethyl carbonate 1:1 (w/w))
The advantages of the new methods and the therewith produced coated LiEAM are the enhanced purity due to the specific reactants. In addition, most of the carbon coating methods are performed via pyrolysis under reducing conditions in order to avoid combustion instead of pyrolysis. Therefore, it is impossible to coat numerous cathode materials which are in a high oxidation state with these methods. A separate reduction/coating will reduce the oxidation state and therefore make the EAM unuseable for cathodes.
In case of the one step method disclosed in U.S. Pat. No. 6,962,666 one advantage of the present method is also that due to the inventive reactions no pyrolysis takes place. Another advantage is the enhanced purity and reproducibility due to the use of metallated reductants.
In one embodiment these reductants may be free from oxygen and optionally free from oxygen and hydrogen which may result in better defined coatings and insertion/intercalation products.
The method of the invention is a surface contact reaction. Thus, due to the specific starting materials and reaction conditions according to the invention only the EAM is coated. Possible non-EAM side-products, e.g. impurities from EAM production, can be found during the coating reaction (e.g. optically due to having a colour different from black) and separated from the product if desired. Furthermore the atom economy of the reaction is 100% or at least close to 100%, i.e. no metal or surface coating atom is wasted during the reaction. Compared to a pyrolysis method the method of the invention is a very environment friendly reaction due to the lower energy consumption and the about 100% atom economy. Especially if oxygen free reductants are used, no waste management of the exhaust (CO, NOx) is needed.
Another advantage of the method of the invention is that no solvent is needed in the inventive coating reaction although in some cases use of a solvent might be useful.
The methods of the present invention lead to a predictable conversion of the coating precursor to the desired coating and predictable Li ions insertion since the reactions are stoichiometric. The invention also provides reactions that can be performed at low temperature and therefore are also suitable for coating temperature sensitive EAMs.
Contrary thereto the pyrolysis reaction of carboxylic acid salts will, dependent on the conditions and a specific EAM, in general lead to different compounds and to less defined coatings.
A further advantage of the inventive methods is that they can be used to produce a variety of conductive non carbonaceous coatings.
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings, that show:
Galvanostatic measurements were monitored by Astrol, a program from Astrol Electronic AG. A potentiostat (BAT-SMAL, battery cycler) was connected using a serial cable to a personal computer (running Windows XP) via a serial/analog converter. The composition of all electrodes was 73% active material, 15% Super P® Carbon (obtainable from TIMCAL) and 2% polyvinylidene fluoride (PVDF). The materials were mixed in a THF/Toluene 4:1 mixture. Finally the electrodes were dried at 180° C. under air. The only exception was the LiFePO4 electrode that was dried at 80° C. under vacuum. The measurements were done with fixed currents of 50 A/kg.
The electrolyte was LP30 (obtainable from Merck Chemicals), 1.4 mol/L LiPF6 in ethylene carbonate/dimethyl carbonate 1/1 by weight. and the counter electrode was a disk of metallic lithium with a diameter of 13 mm and 0.5 mm thickness.
The measurements were performed with a Netzsch STA 409 using corundum crucibles using a heating rate of 10 K/min. The reference powder was corundum, too. The measurements show (see
The measurements were performed with a STOE STADI P2 diffractometer in transmission mode with germanium monochromator, CUka1=1.54056 A
Electron microscopy was performed in a Tecnai F30 microscope (manufactured by FEI) with a field emission gun (FEG), Vacc=300 kV, and Cs=1.2 mm
1.5 Li2C2+10 V2O5→10 Li0.3V2O5+3 Csurface
1.8 g (10 mmol) V2O5 and 0.0569 g (1.5 mmol) Li2C2 were mixed in a mortar. Then the mixture was heated to 600° C. using a heating ramp of 180° C./h and kept at 600° C. for 0.5 hours.
5 Li2C2+10 V2O5→10 LiV2O5+10 Csurface
1.8 g (10 mmol) V2O5 and 0.1895 g (5 mmol) Li2C2 were mixed in a mortar. Then the mixture was heated to 600° C. using a heating ramp of 180° C./h and kept at 600° C. for 0.5 hours.
3 Li2C2+6 FePO4→6 LiFePO4+6 Csurface
0.905 g (6 mmol) FePO4 and 0.114 g (3 mmol) Li2C2 were mixed in a mortar. Then the mixture was heated to 450° C. using a heating ramp of 180° C./h and kept at 450° C. for 2 hours.
The starting materials indicated below were premixed in a mortar before reacted in a Fritsch Pulverisette 6 with 400 rpm for 0.5 hours and at a ratio between the weight of the balls and the weight of the sample of 1:5.
5 Li2C2+10 V2O5→10 LiV2O5+10 Csurface
1.8 g (10 mmol) V2O5 and 0.1895 g (5 mmol) Li2C2 were premixed in a mortar. Then the mixture was reacted in a Fritsch Pulverisette 6 with 400 rpm for 0.5 hours.
1.5 Li2C2+10 MoO3→10 Li0.3MoO3+3 Csurface
1.4394 g (10 mmol) MoO3 and 0.0569 g (1.5 mmol) Li2C2 were premixed in a mortar. Then the mixture was reacted in a Fritsch Pulverisette 6 with 400 rpm for 0.5 hours.
5 Li2C2+10 H2V3O8→10 LiH2V3O8+10 Csurface
2.8284 g (10 mmol) H2V3O8 and 0.1895 g (5 mmol) Li2C2 were premixed in a mortar. Then the mixture was reacted in a Fritsch Pulverisette 6 with 400 rpm for 0.5 hours.
From the coated particulate materials described above electrodes were prepared by mixing 73% coated LiEAM 15% Super P® Carbon (obtainable from TIMCAL) and 2% polyvinylidene fluoride (PVDF) in a THF/Toluene 4:1 mixture and then drying at 180° C. under air, except for the LiFePO4 electrode that was dried at 80° C. under vacuum.
Analytical data and electrochemical behaviour is shown in the Figures as indicated to each example.
While there are shown and described presently preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto but may be otherwise variously embodied and practiced within the scope of the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 11195377.4 | Dec 2011 | EP | regional |
| 12157429.7 | Feb 2012 | EP | regional |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 14741641 | Jun 2015 | US |
| Child | 15848745 | US | |
| Parent | 13724748 | Dec 2012 | US |
| Child | 14741641 | US |
