Patent Application
20240234818
The present disclosure relates to the technical field of lithium batteries, and more particularly, to an electrolyte, a battery cell, a battery, and an electrical device.
Metal negative secondary battery has much higher volumetric energy density than conventional secondary battery, and thus it has great application potential in high-endurance electric vehicles, unmanned aerial vehicles, electric aircraft and other application scenarios. However, such batteries also have disadvantages such as poor circulation ability, poor low-temperature capacity release ability, and the like, as compared with the conventional secondary battery.
There is a need in the art for an electrolyte that can improve the cycling performance of a metal negative secondary battery and improve its low temperature performance at the same time.
The present disclosure has been made in view of the above-mentioned problems, and an object thereof is to provide an electrolyte, which enables a metal negative secondary battery to have an excellent cycle life and a significantly improved low-temperature capacity release capability.
A first aspect of the present disclosure provides an electrolyte, containing a solvent, including at least one compound of formula I.
The electrolyte of the present disclosure enables a metal negative secondary battery to have good cycling performance and good discharge capacity retention rate at low temperatures over a wide temperature range.
In an embodiment, R1 and R2 are each independently a hydrogen atom, C1-C4 alkyls or C1-C4 fluoroalkyls; optionally, R1 and R2 are each independently a hydrogen atom, a methyl, or a fluoromethyl; more optionally, R1 and R2 are each independently a hydrogen atom or a fluoromethyl; still more optionally, R1 and R2 are each independently a hydrogen atom.
In an embodiment, R3 and R4 are each independently a hydrogen atom, a fluorine atom, C1-C4 alkyls and C1-C4 fluoroalkyls; optionally, R3 and R4 are each independently a hydrogen atom, a fluorine atom, a methyl, or a fluoromethyl.
In an embodiment, R3 is a fluorine atom or a hydrogen atom, optionally a fluorine atom.
In an embodiment, in each formula, R4 is a hydrogen atom.
Further selecting the respective groups in the above-mentioned compound of formula I make the electrolyte of the present disclosure have good oxidation resistance, can effectively dissociate the electrolyte salts, and is more conducive to improving the cycling performance of the secondary battery over a wide temperature range and having a desirable discharge capacity at a low temperature.
In an embodiment, the compound of formula I is selected from at least one of the following compounds:
The inclusion of the above-mentioned compounds in the electrolyte of the present disclosure can be more beneficial to improve the cycling performance and low-temperature discharge capacity retention rate of the secondary battery.
In an embodiment, the solvent further comprises one or more selected from: ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, butylene glycol dimethyl ether, dimethoxymethane, diethoxymethane, trimethyl orthoformate, triethyl orthoformate, trimethyl orthocarbonate, triethyl orthocarbonate, ethylene carbonate, vinylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, fluoroethylene carbonate, acetonitrile, dimethyl sulfoxide, sulfolane, bis(2,2,2-trifluoroethyl) ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,2-bis(1,1,2,2-tetrafluoroethoxy) ethane, fluorobenzene, p-difluorobenzene, o-difluorobenzene, m-difluorobenzene, trifluorobenzene, trifluorotoluene, trifluoromethoxybenzene, acetone and perfluoropentanone; optionally, the solvent further comprises dimethyl carbonate and/or perfluoropentanone.
In an embodiment, the solvent includes at least 20 wt %, more optionally at least 60 wt % of the compound of formula I, based on a total weight of the solvent. Using the compound of formula I with the above-mentioned percentages in the electrolyte can achieve high oxidation resistance and high ion transport properties at the same time.
In an embodiment, the electrolyte further includes an additive selected from at least one of: succinic anhydride, vinylene carbonate, 1,3-propane sultone, ethylene vinyl carbonate, fluoroethylene carbonate, vinyl sulfite, tris(trimethylsilane) phosphate.
In an embodiment, a content of the additive is 5 wt % or less based on the total weight of the electrolyte.
The use of the additives is conducive to further improving the battery performance.
In an embodiment, the electrolyte further includes an electrolyte salt selected from at least one of lithium bis-fluorosulfonimide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium bis-trifluoromethane sulfonimide, lithium triflate, lithium difluorophosphate, lithium bis(oxalate) borate, lithium difluorooxalato borate, lithium bis(oxalate) phosphate, and lithium tetrafluorooxalato phosphate; optionally, at least one of lithium difluorosulfonamide, lithium hexafluorophosphate, and lithium tetrafluoroborate; more optionally, lithium bis-fluorosulfonimide. The use of the above-mentioned electrolyte salt is more conducive to improving the cycling performance of the metal negative secondary battery and improving the discharge capacity retention of the battery under low-temperature conditions.
In an embodiment, the concentration of the electrolyte salt is 0.5 M to 5 M, optionally 1 M to 3 M, more optionally 1.5 M to 2.5 M. Controlling the electrolyte salt concentration in the above-mentioned range is more conducive to improving the cycling performance and low-temperature performance of the secondary battery.
A second aspect of the present disclosure provides a battery cell including the electrolyte of the first aspect of the present disclosure.
In an embodiment, the battery cell further includes a negative electrode plate comprising a current collector and optionally a layer of negative material disposed on at least one surface of the current collector, wherein the negative material is a lithium-containing metal; optionally, the lithium-containing metal is simple lithium metal or a lithium-containing alloy; the lithium-containing alloy is an alloy formed by lithium and other metallic elements or non-metallic elements, wherein the metallic elements include tin (Sn), zinc (Zn), aluminum (Al), magnesium (Mg), silver (Ag), gold (Au), gallium (Ga), indium (In), and platinum (Pt), and combinations thereof, the non-metallic elements include boron (B), carbon (C), and silicon (Si) and combinations thereof.
A third aspect of the present disclosure provides a battery including the battery cell of the second aspect of the present disclosure.
A fourth aspect of the present disclosure provides an electrical device, including the battery cell of the second aspect and/or the battery of the third aspect.
The electrolyte of the present disclosure enables a metal negative secondary battery to have an excellent cycle life and a significantly improved low-temperature capacity release capability.
1 battery pack; 2 upper box; 3 lower box; 4 battery module; 5 secondary battery; 51 housing; 52 electrode assembly; 53 top cover assembly
Hereinafter, embodiments of an electrolyte, a secondary battery, a battery module, a battery pack, and an electrical device of the present disclosure are specifically disclosed with reference to the accompanying drawings as appropriate. However, there may be cases where unnecessary detailed description is omitted. For example, detailed descriptions of well-known matters and repeated descriptions of practically identical structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the drawings and the following description are provided to enable those skilled in the art to fully understand the present disclosure and are not intended to limit the subject matter recited in the claims.
The “ranges” disclosed herein are defined in terms of lower and upper limits, a given range is defined by selecting a lower limit and an upper limit, and the selected lower and upper limits define the boundaries of the particular range. Ranges defined in this manner may or may not be inclusive of the end values and can be arbitrarily combined, i.e. any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. In addition, if the minimum range values listed are 1 and 2, and if the maximum range values listed are 3, 4, and 5, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present disclosure, unless otherwise indicated, the numerical range “a-b” represents an abbreviated representation of any real number combination between a and b, where a and b are both real numbers. For example, a numerical range of “0-5” indicates that all real numbers between “0-5” have been fully set forth herein, and “0-5” is merely a shorthand representation of combinations of these numbers. In addition, when it is stated that a certain parameter is an integer of ≥2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.
All embodiments and alternative embodiments of the present disclosure may be combined with each other to form a new technical solution if not specifically stated.
All technical features and alternative technical features of the present disclosure may be combined with each other to form a new technical solution if not specifically stated.
Unless otherwise specified, all steps of the present disclosure may be performed sequentially or may be performed randomly, preferably sequentially. For example, the process comprises steps (a) and (b), meaning that the process may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the reference to the process may further comprise step (c), meaning that step (c) may be added to the process in any order. For example, the process may comprise steps (a), (b) and (c), may also comprise steps (a), (c) and (b), may also comprise steps (c), (a) and (b), etc.
Unless otherwise specified, references to “comprising” and “containing” in the present disclosure are intended to be open-ended as well as closed-ended. For example, reference to “comprising” and “containing” may mean that other components not listed may also be comprised or contained, or that only listed components may be comprised or contained.
In the present disclosure, the term “or” is inclusive if not specifically stated. For example, the phrase “A or B” means “A, B, or both A and B”. More specifically, condition “A or B” is satisfied by any one of the following conditions: A is true (or present) and B is false (or not present); A is false (or absent) and B is true (or present); or both A and B are true (or present).
Metal negative secondary battery has much higher volumetric energy density than conventional secondary battery, and thus it has great application potential in high-endurance electric vehicles, unmanned aerial vehicles, electric aircraft and other application scenarios. However, such batteries also have disadvantages such as poor circulation ability and the like, as compared with the conventional secondary battery.
In order to improve the cycling performance of a metal negative electrode secondary battery (e.g. a lithium metal battery or a sodium metal battery), those skilled in the art have made many efforts in which improvement of an electrolyte is an important aspect. Although the normal-temperature cycling performance of the metal negative secondary battery is improved through the optimization and development of the electrolyte formulation, it is still difficult to maintain good performance over a wide range of working temperature range, and particularly the performance (e.g. cycle life at low temperatures, capacity release ability) of the battery under extreme conditions (especially at low temperatures) is still unsatisfactory.
Currently, the chain ether-based electrolytes commonly used in metal negative secondary batteries are often accompanied by problems of high concentration (i.e. high electrolyte salt concentration), high viscosity, low ionic conductivity, etc. It is very challenging to ensure low-temperature capacity release and long cycle life. Cyclic ether species (e.g. epoxy compounds, particularly tetrahydrofuran and its derivative compounds) have properties that may be advantageous for improving low temperature performance, such as low boiling and freezing points, low viscosity, etc. but such species often have poor oxidation stability, which is not conducive to being used as the primary solvent in an electrolyte.
In view of the problems, there is a need in the art for an electrolyte that can improve both the normal temperature and low temperature performance of a metal negative secondary battery.
An object of the present disclosure is to provide an electrolyte that enables a metal negative secondary battery to have excellent performance (e.g. long cycle life and high capacity release at low temperatures) over a wide temperature range.
An aspect of the present disclosure provides an electrolyte, containing a solvent including at least one compound of formula I.
The electrolyte of the present disclosure enables a metal negative electrode secondary battery to have good normal temperature and low temperature cycling performance and have good discharge capacity retention at low temperature.
Herein, “single bond” has the meaning commonly understood by those skilled in the art and means a covalent bond formed by sharing a pair of electrons between two atoms, usually indicated by a short line “-”.
Herein, “discharge capacity retention rate” is defined as the average capacity release of a battery at 25° C. as C0 and the cycle average capacity release at t° C. as Ct, then the capacity retention is Ct/C0.
Herein, “solvent” has the commonly understood meaning, i.e. a liquid used to dissolve a solute; specifically, in the present disclosure, the solvent is a liquid compound or a mixture thereof for dissolving an electrolyte salt, an additive (if present) and the like contained in an electrolytic solution, and usually occupies an amount of, for example, at least 10% by weight in the electrolyte.
Herein, “low temperature” means a temperature ranging from about −40° C. to about 0° C.
Without wishing to be bound by any theory, the inventors have found that the compounds of formula I of the present disclosure have a 5- or 6-membered ring structure, making them less susceptible to side reactions which will deteriorate the battery performance such as oxidative ring opening, polymerization, etc. during the cycling of the battery due to moderate ring tension and structural stability. At the same time, such a ring structure also enables the compound to have appropriate solvation ability, which is beneficial to maintain a desired discharge capacity of the secondary battery at a lower temperature. When the compound has a ring structure of less than 5-membered (e.g. 3-membered or 4-membered), the ring tension is large, unstable and easily decomposed, while a ring structure of more than 6-membered (e.g. 7-membered and above) has a large volume and poor ion transport property. Thus, they are not an ideal candidate for a solvent. Meanwhile, for the present disclosure, it is advantageous that the substituents of the compound of formula I is are substituents with small volume, for example, a hydrogen atom, a fluorine atom, C1-C6 alkyls or C1-C6 fluoroalkyls, and such substituents with small volume make the compound and the solvent containing the compound have a lower melting boiling point and viscosity, facilitating the maintenance of the discharge capacity of the battery at a low temperature. In addition, the fluorine-containing substituents (including fluoroalkyls and the fluorine atom) in the compound of formula I are necessary to achieve the desired effects of the present disclosure, and such substituents make use of the strong electron-withdrawing effect of the fluorine atom to impart improved oxidation resistance to the compound, which is more favorable for achieving a long-term stable cycle of the metal negative electrode secondary battery. However, at the same time, the inventors have also found that in the compound of formula I of the present disclosure, there is no more than one fluorine-containing substituent, and the fluorine atom cannot be directly substituted on the carbon atom adjacent to the oxygen atom in the ring structure, because the strong electron-withdrawing effect of the fluorine atom causes strong attraction to the lone pair of electrons of the oxygen atom, and therefore a reasonable quantity and position of the fluorine-containing substituents are more conducive to maintaining the ability of the oxygen atom to bind to lithium ions or sodium ions, so that solvent molecules can effectively dissociate (or solvate) electrolyte salts, resulting in a higher ion conductivity in the electrolyte system, thereby improving the low-temperature discharge performance thereof.
In some embodiments, R1 and R2 are each independently a hydrogen atom, C1-C4 alkyls or C1-C4 fluoroalkyls. R1 or R2 is advantageously selected from the group consisting of a hydrogen atom and alkyls or haloalkyls with shorter carbon chains, as such compounds of formula I may have desirably lower melting and boiling points and viscosities, thereby facilitating maintenance of the capacity release capability of the battery at lower temperatures. optionally, the fluoroalkyl is a monofluoroalkyl. In some embodiments, R1 and R2 are each independently a hydrogen atom, a methyl, or a fluoromethyl. Optionally, the fluoromethyl is monofluoromethyl. In some embodiments, R1 and R2 are each independently a hydrogen atom or fluoromethyls. In some embodiments, R1 and R2 are each independently a hydrogen atom.
In some embodiments, R3 and R4 are each independently a hydrogen atom, a fluorine atom, C1-C4 alkyls or C1-C4 fluoroalkyls. R3 or R4 is advantageously selected from the group consisting of a hydrogen atom, a fluorine atom and alkyls or haloalkyls with shorter carbon chains, as such compounds of formula I may have desirably lower melting and boiling points and viscosities, thereby facilitating maintenance of the capacity release capability of the battery at lower temperatures. Optionally, the fluoroalkyl is a monofluoroalkyl. In some embodiments, R3 and R4 are each independently a hydrogen atom, a fluorine atom, a methyl, or a fluoromethyl. Optionally, the fluoromethyl is monofluoromethyl.
In some embodiments, R3 is a fluorine atom or a hydrogen atom; optionally, R3 is a fluorine atom.
In some embodiments, R4 is a hydrogen atom.
Further selecting the above-mentioned compound of formula I having the above-mentioned substituents can make the electrolyte of the present disclosure have good oxidation resistance, can effectively dissociate the electrolyte salt, and is more conductive to improving the cycling performance of the secondary battery over a wide temperature range and having a desirable discharge capacity at a low temperature.
In some embodiments, the solvent includes a compound of formula I selected from one or more of the following compounds:
In some embodiments, the solvent includes at least one of compounds I-1, I-9, I-57, and I-78. In some embodiments, the solvent includes at least one of compounds I-1 and I-78; more optionally, the solvent includes compound I-1. In some embodiments, the solvent includes one or more of the preferred compounds described above. The use of the above-mentioned compound of formula I in the electrolyte of the present disclosure further improves the cycling performance and low-temperature discharge capacity retention rate of the secondary battery due to its good oxidation resistance and electrolyte salt dissociation capability at the same time.
In some embodiments, in the electrolyte the solvent further includes one or more selected from: ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, butylene glycol dimethyl ether, dimethoxymethane, diethoxymethane, trimethyl orthoformate, triethyl orthoformate, trimethyl orthocarbonate, triethyl orthocarbonate, ethylene carbonate, vinylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, fluoroethylene carbonate, acetonitrile, dimethyl sulfoxide, sulfolane, bis(2,2,2-trifluoroethyl) ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, 1,2-bis(1,1,2,2-tetrafluoroethoxy) ethane, fluorobenzene, p-difluorobenzene, o-difluorobenzene, m-difluorobenzene, trifluorobenzene, trifluorotoluene, trifluoromethoxybenzene, acetone and perfluoropentanone. In some embodiments, optionally, the solvent further includes dimethyl carbonate and/or perfluoropentanone. These solvents above have relatively low melting points, good miscibility with the compounds of formula I of the present disclosure and excellent stability to positive and negative electrodes; it can be added thereto to reduce the cost without significantly losing the excellent performance of the battery.
In some embodiments, the solvent includes at least 20 wt %, more optionally at least 60 wt % of the compound of formula I, based on a total weight of the solvent. The inclusion of a compound of formula I in the above-mentioned range in the electrolyte can achieve high oxidation resistance, low viscosity and high ion transport properties at the same time. In some embodiments, the solvent includes at least 60 wt % of the compound of formula I, based on a total weight of the solvent.
In some embodiments, the electrolyte further includes an electrolyte salt, wherein the electrolyte salt is selected from at least one of lithium bis-fluorosulfonimide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium bis-trifluoromethane sulfonimide, lithium triflate, lithium difluorophosphate, lithium bis(oxalato) borate, lithium difluorooxalato borate, lithium difluoro bis(oxalato) phosphate, and lithium tetrafluorooxalato phosphate; optionally, the electrolyte salt is selected from at least one of lithium difluorosulfonamide, lithium hexafluorophosphate, and lithium tetrafluoroborate; more optionally, the fluorine-containing electrolyte salt is lithium bis-fluorosulfonimide. The above-mentioned electrolyte salts can decompose on the surface of the metal negative electrode to form SEI components rich in inorganic fluorine, which is more conducive to improving the cycling performance of the metal negative electrode battery; at the same time, the combination of the above-mentioned electrolyte salt with the compound of formula (I) can impart a higher ionic conductivity and a lower viscosity to the electrolyte, which is further conducive to improving the discharge capacity retention capacity of the secondary battery under low-temperature conditions. Lithium bis-fluorosulfonimide is particularly optional, which can significantly improve the performance of the electrolyte, particularly low temperature performance.
In some embodiments, the electrolyte salt can also be one or more of sodium hexafluorophosphate (NaPF6), sodium hexafluoroborate (NaBF4), NaN(SO2F)2 (abbreviated as NaFSI), NaClO4, NaAsF6, NaB(C2O4)2 (abbreviated as NaBOB), NaBF2(C2O4) (abbreviated as NaDFOB), NaN(SO2RF)2, and NaN(SO2F)(SO2RF), wherein RF represents CbF2b+1 and b is an integer in the range of 1-10, optionally in the range of 1 to 3, more optionally RF is —CF3, —C2F5 or —CF2CF2CF3.
In some embodiments, the concentration of the electrolyte salt is 0.5 M to 5 M, optionally 1 M to 3 M, more optionally 1.5 M to 2.5 M. In some embodiments, the concentration of the electrolyte salt is 2M. Controlling the electrolyte salt concentration in the above-mentioned range can make the electrolyte have better ion transport capacity and more desirable viscosity, which is conducive to improving the interfacial stability of the plates, and further improving the cycling performance and low-temperature performance.
In some embodiments, the electrolyte of the present disclosure also optionally incudes an addictive. For example, the additive may include a negative film-forming additive, a positive film-forming additive, and may further include an additive capable of improving certain properties of the battery, such as an additive for improving overcharge properties of the battery, an additive for improving high-temperature or low-temperature properties of the battery, etc.
In some embodiments, the additive is selected from at least one of: succinic anhydride, vinylene carbonate, 1,3-propane sultone, ethylene vinyl carbonate, fluoroethylene carbonate, vinyl sulfite, tris(trimethylsilane) phosphate.
In some embodiments, a content of the additive is 5 wt % or less based on the total weight of the electrolyte.
The use of the additives is conducive to further improving the battery performance.
In some embodiments, the electrolyte of the present disclosure is used for lithium metal secondary batteries or sodium metal secondary batteries, optionally for lithium metal secondary batteries.
Another aspect of the present disclosure provides a battery cell including the electrolyte described above.
Herein, “battery cell” and “secondary battery” have the same or similar meanings.
In some embodiments, the battery cell of the present disclosure is selected from lithium metal secondary battery cell or sodium metal secondary battery cell.
In some embodiments, the battery cell of the present disclosure further includes a negative electrode plate including a current collector and a layer of negative material disposed on at least one surface of the current collector, wherein the negative material is a lithium-containing or sodium-containing metal; optionally, the negative material is a lithium-containing metal; optionally, the lithium-containing metal is simple lithium metal or a lithium-containing alloy. In some embodiments, optionally, the lithium-containing alloy is an alloy formed by lithium and other metallic elements or non-metallic elements, wherein the metallic elements include tin (Sn), zinc (Zn), aluminum (Al), magnesium (Mg), silver (Ag), gold (Au), gallium (Ga), indium (In), and platinum (Pt), and combinations thereof; the non-metallic elements include boron (B), carbon (C), and silicon (Si) and combinations thereof.
A third aspect of the present disclosure provides a battery pack including the battery cell of the present disclosure. The battery of the present disclosure may be, for example, a battery module or a battery pack.
A fifth aspect of the present disclosure provides an electrical device including the battery cell selected from the present disclosure and/or the battery of the present disclosure.
In addition, the battery cell, battery (including, for example, battery module, battery pack), and electrical device of the present disclosure will be explained with appropriate reference to the attached drawings.
An embodiment of the present disclosure provides a battery cell.
Generally, the battery cell includes a positive electrode plate, a negative electrode plate, an electrolyte, and a separator. During charging and discharging of the battery, active ions are intercalated and deintercalated between the positive electrode plate and the negative electrode plate. The electrolyte serves to conduct ions between the positive electrode plate and the negative electrode plate. The separator is arranged between the positive electrode plate and the negative electrode plate, and mainly serves to prevent short circuit between the positive and negative electrodes, and at the same time it can enable the ions to pass through. The reactive ions are selected from the group consisting of lithium ions and sodium ions.
The positive electrode plate typically includes a positive electrode current collector and a positive film layer disposed on at least one surface of the positive electrode current collector, the positive film layer includes a positive electrode active material.
As an example, the positive electrode current collector has two surfaces opposed in its own thickness direction, and a positive film layer is provided on either or both of the two surfaces opposed to the positive electrode current collector.
In some embodiments, the positive electrode current collector may be a metal foil or a composite current collector. For example, aluminum foil may be used as the metal foil. The composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. The composite current collector may be formed by forming a metallic material (aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, silver alloy, etc.) on a substrate of a high molecular material such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.
In some embodiments, the positive electrode material may use, but is not limited to, a lithium transition metal oxide and/or a lithium phosphate of an olivine structure, a sodium transition metal oxide, a polyanionic compound, and a Prussian blue-based compound as the positive electrode active material.
In some embodiments, the positive electrode active material is selected from lithium transition metal oxides. In some embodiments, the lithium transition metal oxide is selected from lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, or a combination thereof.
Examples of lithium transition metal oxides can include, but are not limited to, at least one of lithium cobalt oxides (e.g. LiCoO2), lithium nickel oxides (e.g. LiNiO2), lithium manganese oxides (e.g. LiMnO2, LiMn2O4), lithium nickel cobalt oxides, lithium manganese cobalt oxides, lithium nickel manganese oxides, lithium nickel cobalt manganese oxides (e.g. LiNi1/3Co1/3Mn3O2 (also referred to as NCM333 for short), LiNi0.5Co0.2Mn0.3O2 (also referred to as NCM523 for short), LiNi0.5Co0.25Mn0.25O2 (also referred to as NCM211 for short), LiNi0.6Co0.2Mn0.2O2 (also referred to as NCM622 for short), LiNi0.5Co0.1Mn0.1O2 (also referred to as NCM811 for short), LiNi0.96Co0.02Mn0.02O2 (also referred to as Ni96 for short), lithium nickel cobalt aluminum oxide (such as LiNi0.85Co0.15Al0.05O2), and modified compounds thereof, and the like.
Examples of the lithium-containing phosphate of the olivine structure may include, but are not limited to, at least one of lithium iron phosphate (such as LiFePO4 (also referred to as LFP for short)), a composite of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO4), a composite of lithium manganese phosphate and carbon, lithium iron manganese phosphate, a composite of lithium iron manganese phosphate and carbon.
In some embodiments, in the sodium transition metal oxide, the transition metal can be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr, and Ce. The sodium transition metal oxide is for example NaxMyO2, wherein M is one or more of Ti, V, Mn, Co, Ni, Fe, Cr, and Cu, 0<x≤1, 0.5<y≤1.5. In some embodiments, Na0.88Cu0.24Fe0.29Mn0.47O2 may be used as the positive electrode active material.
In some embodiments, polyanionic compounds can be a class of compounds having sodium ions, transition metal ions, and tetrahedral (YO4)n− anionic units. The transition metal may be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr, and Ce; Y may be at least one of P, S and Si; N represents the valence of (YO4)n−.
In some embodiment, polyanionic compounds can be a class of compounds having sodium ions, transition metal ions, and tetrahedral (YO4)n− anionic units and halide anions. The transition metal may be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr, and Ce; Y may be at least one of P, S and Si, and n represents the valence of (YO4)n−; and the halogen can be at least one of F, CI, and Br.
In some embodiments, polyanionic compounds can also be a class of compounds having sodium ions, tetrahedral (YO4)n− anionic units, polyhedral units (ZOy)m+, and optionally halide anions. Y may be at least one of P, S and Si, and n represents the valence of (YO4)n−; Z represents a transition metal, which may be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr, and Ce, and m represents the valence of (ZOy)m+; and the halogen can be at least one of F, CI, and Br.
In some embodiments, the polyanionic compound is, for example, at least one of NaFePO4, Na3V2(PO4)3, NaM′PO4F (M′ is one or more of V, Fe, Mn, and Ni), and Na3(VOy)2(PO4)2F3-2y (0≤y≤1).
In some embodiments, the Prussian blue-based compounds may be a class of compounds having a sodium ion, a transition metal ion, and a cyanide ion (CN−). The transition metal can be at least one of Mn, Fe, Ni, Co, Cr, Cu, Ti, Zn, V, Zr, and Ce. Prussian blue-based compounds are for example NaaMebMe′c(CN)6, wherein Me and Me′ are each independently at least one of Ni, Cu, Fe, Mn, Co, and Zn, 0<a≤2, 0<b≤1, 0<c<1.
In some embodiments, the positive film layer also optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), tetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and a fluorine-containing acrylate resin.
In some embodiments, the positive film layer also optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the positive electrode plate can be prepared by: dispersing the above-mentioned components for preparing the positive electrode plate, such as a positive electrode active material, a conductive agent, a binder and any other components, in a solvent (such as N-methyl pyrrolidone) to form a positive electrode slurry; coating the the positive electrode current collector with the positive electrode slurry, and the positive electrode plate can be obtained after drying, cold pressing and other processes.
The negative electrode plate includes a negative electrode current collector and a negative film layer optionally arranged on at least one surface of the negative electrode current collector, wherein the negative film layer includes an negative electrode active material.
As an example, the negative electrode current collector has two surfaces opposed in its own thickness direction, and a negative film layer (if present) is arranged on either or both of the two surfaces opposed to the negative electrode current collector.
In some embodiments, the negative electrode current collector may be a metal foil or a composite current collector. For example, a copper foil may be used as the metal foil. Optionally, the negative current collector is a metal foil, more optionally a copper foil. The composite current collector may include a polymer material substrate and a metal layer formed on at least one surface of the polymer material base layer. The composite current collector may be formed by forming a metallic material (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver, silver alloy, etc.) on a substrate of a high molecular material such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.
In some embodiments, the negative film layer, if present, is a lithium-containing metal or a sodium-containing metal, optionally a lithium-containing metal; optionally, the lithium-containing metal is simple lithium metal or a lithium-containing alloy. The lithium-containing alloy is an alloy formed by lithium and other metallic elements or non-metallic elements, wherein the metallic elements include tin (Sn), zinc (Zn), aluminum (Al), magnesium (Mg), silver (Ag), gold (Au), gallium (Ga), indium (In), and platinum (Pt), and combinations thereof; the non-metallic elements include boron (B), carbon (C), and silicon (Si) and combinations thereof. Optionally, the lithium-containing alloy is an alloy of lithium with other metallic elements or non-metallic elements, wherein the metallic elements include tin (Sn), zinc (Zn), aluminum (Al), magnesium (Mg), silver (Ag), gold (Au), gallium (Ga), indium (In), and platinum (Pt), and combinations thereof; the non-metallic elements include boron (B), carbon (C), and silicon (Si) and combinations thereof.
In some embodiments, the negative electrode plate includes a negative current collector and a negative film layer arranged on at least one surface of the negative current collector. The negative film layer includes lithium/sodium metal substances as negative electrode active materials. In some embodiments, the negative film layer is lithium foil.
In some embodiments, the plate is prepared by applying a lithium-containing metal foil or a sodium-containing metal foil as a negative film layer to at least one surface of a negative electrode current collector by, for example, rolling and the like to form a negative electrode plate.
In some embodiments, the secondary battery further includes a separator. There is no particular limitation on the kind of the separator in the present disclosure, and any known separator with a porous structure having good chemical stability and mechanical stability can be selected.
In some embodiments, the separator may use, not limited to, a polyethylene porous film, a polypropylene porous film, a polyimide porous film, and a porous film compounded by various polymers.
The separator may be a single-layer film or a multi-layer composite film, without particular limitation. When the separator is a multilayer composite film, the materials of each layer may be the same or different, without particular limitation.
In some embodiments, the positive electrode plate, the negative electrode plate, and the separator can be made into an electrode assembly by a winding process or a lamination process.
In some embodiments, the battery cell may include an outer package. The outer package may be used to encapsulate the electrode assembly and the electrolyte.
In some embodiments, the outer package of the battery cell may be a hard case such as a hard plastic case, an aluminum case, a steel case, and the like. The outer package of the battery cell may also be a soft package, such as a pouch-type soft package. The material of the soft bag may be plastic, and as the plastic, polypropylene, polybutylene terephthalate, polybutylene succinate, etc. may be listed.
The shape of the battery cell is not particularly limited in the present disclosure, and may be cylindrical, square or any other shape. For example,
In some embodiments, referring to
In some embodiments, the battery cell can be assembled into a battery module or a battery pack, and the number of secondary batteries contained in the battery module or battery pack can be one or more, and the specific number can be selected by a person skilled in the art according to the application and capacity of the battery module.
Optionally, the battery module 4 may further include a housing having a accommodating space in which the plurality of battery cells 5 are received.
In some embodiments, the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be one or more, and the specific number can be selected by a person skilled in the art according to the application and capacity of the battery pack.
In addition, the present disclosure also provides an electrical device including at least one of the secondary battery, the battery module, or the battery pack provided herein. The secondary battery, the battery module, or the battery pack may be used as a power source for the electrical device as well as an energy storage unit for the electrical device. The electrical device may include, but not limited to, mobile equipment (e.g. cell phones, notebook computers, etc.), electric vehicles (e.g. pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc.
As the electrical device, the secondary battery, the battery module, or the battery pack may be selected according to its usage requirements.
As another example, the device may be a cell phone, tablet computer, notebook computer, etc. The device is generally required to be light and thin, and a secondary battery may be used as a power source.
Hereinafter, examples of the present disclosure will be described. The examples described below are exemplary and are intended to be illustrative of the present disclosure and are not to be construed as limiting the present disclosure. Where specific techniques or conditions are not specified in the examples, they are performed according to techniques or conditions described in the literature or in the art or according to the product manual. The reagents or instruments used, without indicating the manufacturer, are conventional products commercially available.
1.87 g of lithium bisfluorosulfonimide was taken, added into 5 ml of solvent of formula I-1, and stirred thoroughly to form a colorless transparent solution with concentration of electrolyte salt of 1M, which was the electrolyte of the present disclosure.
The lithium foil with a thickness of 50 m was applied to one surface of a copper foil with a thickness of 12 m by rolling, and then cut into a rectangular shape of 41 mm*51 mm to be used as a negative electrode plate.
The positive electrode active material LiNi0.8Co0.1Mn0.1O2(NCM811) (NMC), the conductive agent acetylene black and the binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 98:1:1, a solvent N-methyl pyrrolidone (NMP) is added and stirred until the system was uniform to obtain a positive electrode slurry (with a solid content of 70%); the positive electrode slurry was evenly double-coated on the positive electrode current collector aluminum foil at a loading of about 25 mg/cm2, dried at room temperature, transferred to an oven for further drying, and then cut into a rectangle of 40 mm*50 mm as the positive electrode plate.
The polyethylene porous membrane was selected and cut into a rectangle of 45 mm*55 mm for future use.
A cut positive electrode plate was taken and matched with two cut negative electrode plates. One side of the negative electrode plate covered with lithium foil on faces the positive electrode plate, and the positive and negative electrode plates were separated by the aforementioned separator between them, and wrapped in an aluminum plastic film bag to form a laminated dry cell. 0.3 g of the electrolyte prepared as described above was injected, and vacuum hot-press packaging was performed on the aluminium-plastic film bag; after standing at room temperature for at least 6 hours, the cycle test can be started. The laminated battery thus prepared had a rated capacity of 140 mAh.
The battery prepared as above was taken, charged at 25° C. at an ambient temperature using a constant current with a rate of 0.2 C (namely, 28 mA) to reach a cut-off voltage of 4.3V, then charged with a constant voltage of 4.3V until the current decays to 0.1 C (namely, 14 mA), and then discharged at a rate of 1 C (namely, 140 mA) to 2.8 V, namely, a cycle of charge and discharge. Charge-discharge cycles were performed as such, and the discharge capacity of each cycle was tested. When the discharge capacity of a certain number of cycle decays to 80% of the first cycle discharge capacity, the battery life was considered to be cut-off, while the number of cycles at this time was the cycle life. The results of the tests were shown in Table 1.
The batteries prepared above were placed in a Vötsch VT4044 high and low temperature chamber. First, the temperature of the high and low temperature chamber was set to 25° C., and charge/discharge cycles were performed for 2 cycles in the manner described in (1) above to activate the battery cells. Then, the temperatures of high and low chambers were set to −40° C. and 25° C., respectively, and charge-discharge cycles were performed for 3 cycles in the manner described in (1) above, and the discharge capacity per cycle was recorded, and the average value was calculated.
The low-temperature capacity retention rate was calculated using the following formula:
The test results were shown in Table 1 below.
The cell prepared as above was taken and placed in Vötsch VT4044 high and low temperature test chamber, the temperature of high and low temperature chamber was set as −40° C., charge-discharge cycle was performed in the manner as described in (1) above, and the discharge capacity of each cycle was recorded. When the discharge capacity of a certain number of cycle decays to 80% of the first cycle discharge capacity, the battery life was considered to be cut-off, while the number of cycles at this time was the cycle life of the battery. The results of the tests were shown in Table 1.
The preparation and testing methods of Examples 2-7 were similar to those of Example 1, except that the concentration of electrolyte salt was different, as shown in Table 1.
The preparation and testing methods and the concentration of electrolyte salt of Examples 8-14 were similarly to those of Examples 1-7, respectively, except that the compound of Formula I was I-9, as detailed in Table 1.
The preparation and testing methods and the concentration of electrolyte salt of Examples 15-21 were similarly to those of Examples 1-7, respectively, except that the compound of Formula I was I-57, as detailed in Table 1.
The preparation and testing methods and the concentration of electrolyte salt of Examples 22-28 were similarly to those of Examples 1-7, respectively, except that the compound of Formula I was I-78, as detailed in Table 1.
The preparation and testing methods of Examples 29-31 were similar to those of Example 1 except that compounds of Formula I were I-56, I-73 and I-143, respectively, as detailed in Table 1.
The preparation and testing methods of Examples 32-33 were similar to those of Example 1 except that the electrolyte salt was different, as detailed in Table 1.
In Examples 34-36, the preparation of the electrolyte was as follows:
First, the compound of formula I-1 was mixed with dimethyl carbonate (DMC) in a mass ratio of 1:5 to form a homogeneous mixed solvent; 1.87 g of lithium bisfluorosulfonimide salt (LiFSI) was added to 5 ml of the above-mentioned mixed solvent to form a uniform solution with a concentration of 2M, which was used as an electrolyte for subsequent tests.
The remainder of the preparation and testing methods was similar to Example 1.
The preparation and testing methods of Comparative Example 1 were similar to Example 1 except that the solvent was tetrahydrofuran, as detailed in Table 1.
The preparation and testing methods of Comparative Example 2 were similar to Example 1 except that the solvent was 1,3-dioxolane, as detailed in Table 1.
The preparation and testing methods of Comparative Example 3 were similar to Example 1 except that the solvent was 1,3-dioxane as detailed in Table 1.
The preparation and testing methods of Comparative Example 4 were similarly to Example 1, except that the electrolyte salt was weighed in an amount of 0.28 g and the final concentration was 0.3M, as detailed in Table 1.
The preparation and testing methods of Comparative Example 5 were similarly to Example 1, except that the electrolyte salt was weighed in an amount of 5.61 g and the final concentration was 6M, as detailed in Table 1.
1 The mass percent (or weight percent) is based on the total mass of solvent in the electrolyte.
By comparing each example with the comparative examples, it can be found that if the solvent molecules do not undergo fluorine substitution, and the capacity at low temperature still has a certain capacity retention ability, but the circulation capacity at room temperature and low temperature is significantly poor. In addition, compared with other lithium salts, lithium bis-fluorosulfonimide salts can promote capacity release and long cycle life at low temperature.
The electrolytes of the present disclosure can impart a longer cycle life (up to 402 cycles at room temperature) and good low-temperature performance (good capacity retention at −40° C. and longer cycle life) to a liquid lithium metal secondary battery, and thus can work in a wider temperature range (especially in a harsh environment at −40° C.). In particular, the electrolytes of the present disclosure, can still impart long cycle life to secondary batteries even at relatively low temperatures, wherein the cycle life can remain keep above 130 cycles (and in some examples, it can even reach above 280 cycles) under the environment of −40° C. and the charge-discharge conditions of 0.2 C-1 C.
It should be noted that the present disclosure is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and within the scope of the technical solution of the present disclosure, embodiments having substantially the same constitution as the technical idea and exerting the same function and effect are all included within the technical scope of the present disclosure. In addition, various modifications may be made to the embodiments by those skilled in the art without departing from the spirit of the present disclosure, and other embodiments that are constructed by combining some of the constituent elements of the embodiments are also included in the scope of the present disclosure.
This application is a continuation of International Application PCT/CN2022/125067 filed Oct. 13, 2022, the subject matter of which is incorporated herein by reference in its entirety.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2022/125067 | Oct 2022 | WO |
| Child | 18589233 | US |
