CN116130771A - Nonaqueous electrolyte and lithium ion battery thereof - Google Patents

Nonaqueous electrolyte and lithium ion battery thereof Download PDF

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CN116130771A
CN116130771A CN202310068551.0A CN202310068551A CN116130771A CN 116130771 A CN116130771 A CN 116130771A CN 202310068551 A CN202310068551 A CN 202310068551A CN 116130771 A CN116130771 A CN 116130771A
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compound
unsubstituted
halogen
substituted
electrolyte
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刘孟
张昌明
李枫
胡大林
廖兴群
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Huizhou Highpower Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

The invention discloses a non-aqueous electrolyte and a lithium ion battery thereof, wherein the non-aqueous electrolyte comprises lithium salt, an organic solvent and an additive, and the additive comprises a compound A containing a 6-membered ring and/or a cyclic anhydride compound B; the content of the compound A is 0.5 to 5 percent of the total weight of the electrolyte, and the content of the cyclic anhydride compound B is 0.2 to 0.8 percent of the total weight of the electrolyte; the structural formula of the compound A is shown as the following formula (1), and the structural formula of the cyclic anhydride compound B is shown as the following formula (2) or formula (3):

Description

Nonaqueous electrolyte and lithium ion battery thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a non-aqueous electrolyte and a lithium ion battery thereof.
Background
A lithium ion battery is a secondary battery (rechargeable battery) that operates mainly by means of lithium ions moving between a positive electrode and a negative electrode. During charge and discharge, li + To-and-fro intercalation and deintercalation between two electrodes: during charging, li + Is separated from the positive electrode and subjected to electrolysisA cathode is embedded in the anode, and the cathode is in a lithium-rich state; the opposite is true when discharging.
However, as the limiting voltage of the positive electrode material is continuously increased, the gram capacity of the battery material is gradually increased, the high-temperature performance of the battery is seriously deteriorated, the long cycle life cannot be ensured, particularly, the volume of the material is expanded and serious cracks are caused in the long-term cycle charge and discharge process under high voltage (more than 4.5V), the solvent in the electrolyte enters the inside of the positive electrode material, the structure is damaged, and finally, the problems of serious capacity attenuation and thickness expansion are caused.
Therefore, there is a need for a nonaqueous electrolyte solution that can improve the cycle performance of lithium ion batteries at high energy densities, improve the capacity retention rate, and reduce the thickness expansion rate.
Disclosure of Invention
The invention aims to provide a nonaqueous electrolyte and a lithium ion battery thereof, which can improve the cycle performance of the lithium ion battery under high energy density, improve the capacity retention rate and have low thickness expansion rate.
The invention discloses a non-aqueous electrolyte, which comprises lithium salt, an organic solvent and an additive, wherein the additive comprises a compound A containing a 6-membered ring and/or a cyclic anhydride compound B; the content of the compound A is 0.5 to 5 percent of the total weight of the electrolyte, and the content of the cyclic anhydride compound B is 0.2 to 0.8 percent of the total weight of the electrolyte; the structural formula of the compound A is shown as the following formula (1), and the structural formula of the cyclic anhydride compound B is shown as the following formula (2) or formula (3):
Figure BDA0004062980760000021
wherein in formula (1), R1, R2, R3, R4 are each independently selected from C1-C20 alkyl substituted or unsubstituted by halogen, C3-C20 cycloalkyl substituted or unsubstituted by halogen, phenyl substituted or unsubstituted by halogen, C1-C20 alkylene substituted or unsubstituted by halogen, biphenyl substituted or unsubstituted by halogen, C6-C26 phenylalkyl substituted or unsubstituted by halogen, C6-C26 condensed ring aralkyl substituted or unsubstituted by halogen, and a null bond; wherein the number of carbon atoms attached to the-CN and O atoms is C1-C12;
in the formula (2) and the formula (3), R5, R6, R7 and R8 are independently selected from C1-C20 alkyl substituted or unsubstituted by halogen, C3-C20 cycloalkyl substituted or unsubstituted by halogen, phenyl substituted or unsubstituted by halogen, C1-C20 alkylene substituted or unsubstituted by halogen, biphenyl substituted or unsubstituted by halogen, C6-C26 phenylalkyl substituted or unsubstituted by halogen, C6-C26 condensed ring aromatic hydrocarbon substituted or unsubstituted by halogen and empty bond.
Optionally, the additive is a compound A, and the content of the compound A is 1% of the total weight of the electrolyte.
Optionally, the additive package is a cyclic anhydride compound B, and the content of the cyclic anhydride compound B is 0.5% of the total weight of the electrolyte.
Optionally, the additive comprises a compound A and a cyclic anhydride compound B; the content of the compound A is 1% of the total weight of the electrolyte, and the content of the cyclic anhydride compound B is 0.5% of the total weight of the electrolyte.
Optionally, the organic solvent is selected from at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl formate, ethyl propionate, propyl propionate, methyl butyrate, and tetrahydrofuran.
Optionally, the organic solvent comprises ethylene carbonate, propylene carbonate, diethyl carbonate, propyl propionate, and the mass ratio of the ethylene carbonate, the propylene carbonate, the diethyl carbonate and the propyl propionate is 1:1:2:6.
The invention also discloses a lithium ion battery, which comprises the non-aqueous electrolyte.
Optionally, the lithium ion battery further comprises a positive plate, the positive plate comprises a positive current collector and a positive active slurry layer positioned on the positive current collector, the positive active slurry layer comprises a positive active material, and the positive active material is one or more selected from lithium cobaltate, lithium nickel manganese cobalt ternary materials, lithium iron phosphate and lithium manganate.
The nonaqueous electrolyte contains 0.5-5% of compound A and/or 0.2-0.8% of cyclic anhydride compound B, and cyano functional groups (-CN) contained in the compound A can well stabilize the interface property of an anode electrode/electrolyte and inhibit the dissolution of transition metal ions and the further oxidative decomposition of electrolyte components; the unsaturated double bond can also form a polymer at the positive electrode to form a protection for the positive electrode, meanwhile, the electronic structure of the contained pyran is similar to that of benzene, the oxygen atom in the ring has extremely strong alkalinity, and the unsaturated double bond can be combined with F in LiPF6 of lithium salt to form a salt, namely the salt is stabilized. The cyclic anhydride compound B is an anhydride type compound, can be combined with trace water in electrolyte, can avoid excessive HF generated in the later period of lithium ion battery circulation and erode an anode-cathode interface film, and can form a layer of compact CEI film on the surface of an anode to cooperate with the additive A to jointly protect the interface film of the anode. When the compound A and the cyclic anhydride compound B are respectively and independently added, the cycle performance of the lithium ion battery under high energy density can be improved, the capacity retention rate is improved, and the thickness expansion rate is low. The effect of the combination of the two is better than that of the single use of the two.
Detailed Description
It is to be understood that the terminology used herein, the specific structural and functional details disclosed are merely representative for the purpose of describing particular embodiments, but that the invention may be embodied in many alternate forms and should not be construed as limited to only the embodiments set forth herein.
The following optional examples illustrate the invention in detail.
As an embodiment of the present invention, a nonaqueous electrolytic solution is disclosed, the nonaqueous electrolytic solution comprising a lithium salt, an organic solvent and an additive, the additive comprising a 6-membered ring-containing compound a and/or a cyclic acid anhydride-based compound B; the content of the compound A is 0.5 to 5 percent of the total weight of the electrolyte, and the content of the cyclic anhydride compound B is 0.2 to 0.8 percent of the total weight of the electrolyte; the structural formula of the compound A is shown as the following formula (1), and the structural formula of the cyclic anhydride compound B is shown as the following formula (2) or formula (3):
Figure BDA0004062980760000051
/>
wherein in formula (1), R1, R2, R3, R4 are each independently selected from C1-C20 alkyl substituted or unsubstituted by halogen, C3-C20 cycloalkyl substituted or unsubstituted by halogen, phenyl substituted or unsubstituted by halogen, C1-C20 alkylene substituted or unsubstituted by halogen, biphenyl substituted or unsubstituted by halogen, C6-C26 phenylalkyl substituted or unsubstituted by halogen, C6-C26 condensed ring aralkyl substituted or unsubstituted by halogen, and a null bond; wherein the number of carbon atoms bonded to the-CN and O atoms is C1-C12.
In the formula (2) and the formula (3), R5, R6, R7 and R8 are independently selected from C1-C20 alkyl substituted or unsubstituted by halogen, C3-C20 cycloalkyl substituted or unsubstituted by halogen, phenyl substituted or unsubstituted by halogen, C1-C20 alkylene substituted or unsubstituted by halogen, biphenyl substituted or unsubstituted by halogen, C6-C26 phenylalkyl substituted or unsubstituted by halogen, C6-C26 condensed ring aromatic hydrocarbon substituted or unsubstituted by halogen and empty bond.
The nonaqueous electrolyte contains 0.5-5% of compound A and/or 0.2-0.8% of cyclic anhydride compound B, and cyano functional groups (-CN) contained in the compound A can well stabilize the interface property of an anode electrode/electrolyte and inhibit the dissolution of transition metal ions and the further oxidative decomposition of electrolyte components; the unsaturated double bond can also form a polymer at the positive electrode to form a protection for the positive electrode, meanwhile, the electronic structure of the contained pyran is similar to that of benzene, the oxygen atom in the ring has extremely strong alkalinity, and the unsaturated double bond can be combined with F in LiPF6 of lithium salt to form a salt, namely the salt is stabilized. The cyclic anhydride compound B is an anhydride type compound, can be combined with trace water in electrolyte, can avoid excessive HF generated in the later period of lithium ion battery circulation and erode an anode-cathode interface film, and can form a layer of compact CEI film on the surface of an anode to cooperate with the additive A to jointly protect the interface film of the anode. When the compound A and the cyclic anhydride compound B are respectively and independently added, the cycle performance of the lithium ion battery under high energy density can be improved, the capacity retention rate is improved, and the thickness expansion rate is low. The effect of the combination of the two is better than that of the single use of the two.
Specifically, the compound a may account for 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% of the total weight of the electrolyte. Preferably, the additive is compound a, and the content of compound a is 1% of the total weight of the electrolyte.
Specifically, the cyclic anhydride compound B may account for 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% of the total weight of the electrolyte. Preferably, the additive package is a cyclic anhydride compound B, and the content of the cyclic anhydride compound B is 0.5% of the total weight of the electrolyte.
Specifically, the additive comprises a compound A and a cyclic anhydride compound B; the content of the compound A is 1% of the total weight of the electrolyte, and the content of the cyclic anhydride compound B is 0.5% of the total weight of the electrolyte.
Specifically, the organic solvent is at least two selected from ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl formate, ethyl propionate, propyl propionate, methyl butyrate and tetrahydrofuran. Preferably, the organic solvent comprises ethylene carbonate, propylene carbonate, diethyl carbonate, propyl propionate, and the mass ratio of the ethylene carbonate, the propylene carbonate, the diethyl carbonate and the propyl propionate is 1:1:2:6.
Specifically, the electrolyte lithium salt is at least one selected from hexafluorophosphate, hexafluoroarsenate, perchlorate, lithium trifluorosulfonyl, lithium difluoro (trifluoromethylsulfonyl) imide, lithium tris (trifluoromethylsulfonyl) methyl, and lithium difluoroimide sulfonate. Preferably, the electrolyte lithium salt concentration is 0.5M to 1.5M. Specifically, sulfonate compounds, fluorocarbonates and nitrile compounds are also added into the electrolyte.
The invention also discloses a lithium ion battery, which comprises the non-aqueous electrolyte. Specifically, the lithium ion battery further comprises a positive plate, a negative plate and a lithium battery diaphragm. The positive plate comprises a positive current collector and a positive active slurry layer positioned on the positive current collector, wherein the positive active slurry layer comprises a positive active material; the negative electrode sheet comprises a negative electrode current collector and a negative electrode active slurry layer positioned on the negative electrode current collector, wherein the negative electrode active slurry layer comprises a negative electrode active material. The specific types of the positive electrode active material, the positive electrode binder and the negative electrode active material are not particularly limited, and may be selected according to requirements.
Preferably, the positive electrode active material is selected from lithium cobaltate (LiCoO) 2 ) Ternary materials of lithium nickel manganese cobalt, lithium iron phosphate (LiFePO) 4 ) Lithium manganate (LiMn) 2 O 4 ) One or more of the following.
Preferably, the anode active material is graphite and/or silicon, such as natural graphite, artificial graphite, mesocarbon microbeads (abbreviated as MCMB), hard carbon, soft carbon, silicon-carbon composite, li-Sn alloy, li-Sn-O alloy, sn, snO, snO 2 Lithiated TiO of spinel structure 2 -Li 4 Ti 5 O 12 Li-Al alloy can be used as the negative electrode active material.
Further details are provided below by way of specific examples.
Preparation of solution
The preparation steps of the electrolyte are as follows: as the organic solvent, a mass ratio of Ethylene Carbonate (EC)/Propylene Carbonate (PC)/diethyl carbonate (DEC)/Propyl Propionate (PP) =1/1/2/6 was mixed. After adding additives PS and FEC to an organic solvent and uniformly mixing, liPF6 was added to obtain a mixed solution with a concentration of 1.1mol/L LiPF6 to obtain a solution of comparative example 2, and compound A and cyclic anhydride compound B were added to the mixed solution to prepare electrolytes of examples 1 to 5 and comparative example 1 as shown in Table 1. PS is 1, 3-propane sultone, FEC is fluoroethylene carbonate, SN is succinonitrile, ADN is adiponitrile, HTCN is 1,3, 6-hexanetrinitrile. Wherein compound a is selected from the group consisting of:
Figure BDA0004062980760000081
the cyclic anhydride compound B has the following selected structure:
Figure BDA0004062980760000082
experimental protocols for the electrolyte are shown in table 1 below:
TABLE 1
Figure BDA0004062980760000083
/>
Figure BDA0004062980760000091
In table 1, the mass ratio of EC, PC, DEC, PP is PS, FEC, SN, ADN, HTCN, and the contents of the compound a and the cyclic anhydride compound B are percentages of the total weight of the electrolyte.
Manufacturing of battery
Manufacturing a positive plate: and fully stirring and mixing the positive electrode active substance LCO and the conductive agent CNT in an N-methylpyrrolidone solvent according to the weight ratio of 97:1.5:1.5 of the binder polyvinylidene fluoride to form uniform positive electrode slurry. And (3) coating the slurry on an anode current collector Al foil, drying, and cold pressing to obtain the anode plate.
Manufacturing a negative plate: and (3) fully stirring and mixing the negative electrode active material graphite, the conductive agent acetylene black, the adhesive styrene-butadiene rubber and the thickener sodium carboxymethyl cellulose in a proper amount of deionized water solvent according to a mass ratio of 95:2:2:1, so that uniform negative electrode slurry is formed. And (3) coating the slurry on a negative current collector Cu foil, drying, and cold pressing to obtain a negative electrode plate.
Manufacturing a lithium ion battery: and sequentially stacking the positive electrode plate, the isolating film and the negative electrode plate, so that the isolating film is positioned between the positive electrode plate and the negative electrode plate, plays an isolating role, and then winds the bare cell. And (3) placing the bare cell in an outer packaging bag, respectively injecting the electrolyte in the table 1 into the dried battery, and performing the procedures of vacuum packaging, standing, formation, shaping and the like to complete the preparation of the lithium ion battery, thereby sequentially obtaining the battery.
High temperature cycle testing of batteries
The testing method comprises the following steps: and placing the battery in an environment of 45+/-2 ℃, and calculating the capacity retention rate of the battery after circulation according to standard charge-discharge circulation, circulation multiplying power of 1C and charging voltage of 3.0-4.5V.
The calculation formula is as follows:
the nth cycle capacity retention (%) = (nth cycle discharge capacity)/(first cycle discharge capacity) ×100%.
High temperature storage test of battery: the testing method comprises the following steps: and (3) charging the battery core with the separated capacity to 4.5V at normal temperature with a current of 0.5C, placing the full-charge battery in an environment of 85 ℃ for 6 hours, thermally measuring the thickness expansion rate, discharging to 3.0V with a current of 0.5C after the battery core is recovered to room temperature, and recording the discharge capacity.
Battery test conditions are as in table 2:
TABLE 2
Figure BDA0004062980760000101
As can be seen from examples 1-5, and comparative examples 1 and 2 in Table 2, the high temperature cycle and safety performance of example 3 with the addition of compound A alone are best, i.e., the addition of 1% of compound A gives the best results. It can be seen from examples 7 to 8 and comparative example 3 that the effect of example 7 is the best, that is, the effect of the cyclic anhydride compound B content of 0.5% is the best.
Further, in order to verify the combined effect of the additive a and the cyclic anhydride compound B, the following experimental scheme was designed:
Figure BDA0004062980760000111
the test results were as follows:
Figure BDA0004062980760000112
by comparing examples 3, 7 and 10, it is found that the effect of the combination of the compound A and the cyclic anhydride compound B is better than that of the single additive, that is, the combination of the compound A and the cyclic anhydride compound B can jointly improve the electric performance of the battery.
The above description of the invention in connection with specific alternative embodiments is further detailed and it is not intended that the invention be limited to the specific embodiments disclosed. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.

Claims (8)

1. A nonaqueous electrolytic solution characterized by comprising a lithium salt, an organic solvent and an additive comprising a 6-membered ring-containing compound a and/or a cyclic acid anhydride-based compound B; the content of the compound A is 0.5-5% of the total weight of the electrolyte, and the content of the cyclic anhydride compound B is 0.2-0.8% of the total weight of the electrolyte; the structural formula of the compound A is shown as the following formula (1), and the structural formula of the cyclic anhydride compound B is shown as the following formula (2) or formula (3):
Figure FDA0004062980750000011
wherein in formula (1), R1, R2, R3, R4 are each independently selected from C1-C20 alkyl substituted or unsubstituted by halogen, C3-C20 cycloalkyl substituted or unsubstituted by halogen, phenyl substituted or unsubstituted by halogen, C1-C20 alkylene substituted or unsubstituted by halogen, biphenyl substituted or unsubstituted by halogen, C6-C26 phenylalkyl substituted or unsubstituted by halogen, C6-C26 condensed ring aralkyl substituted or unsubstituted by halogen, and a null bond; wherein the number of carbon atoms attached to the-CN and O atoms is C1-C12;
in the formula (2) and the formula (3), R5, R6, R7 and R8 are independently selected from C1-C20 alkyl substituted or unsubstituted by halogen, C3-C20 cycloalkyl substituted or unsubstituted by halogen, phenyl substituted or unsubstituted by halogen, C1-C20 alkylene substituted or unsubstituted by halogen, biphenyl substituted or unsubstituted by halogen, C6-C26 phenylalkyl substituted or unsubstituted by halogen, C6-C26 condensed ring aromatic hydrocarbon substituted or unsubstituted by halogen and empty bond.
2. The nonaqueous electrolyte according to claim 1, wherein the additive is a compound a, and the content of the compound a is 1% by weight of the total electrolyte.
3. The nonaqueous electrolyte according to claim 1, wherein the additive package is a cyclic acid anhydride compound B, and the content of the cyclic acid anhydride compound B is 0.5% by weight based on the total weight of the electrolyte.
4. The nonaqueous electrolytic solution according to claim 1, wherein said additive comprises a compound a and a cyclic acid anhydride-based compound B; the content of the compound A is 1% of the total weight of the electrolyte, and the content of the cyclic anhydride compound B is 0.5% of the total weight of the electrolyte.
5. The nonaqueous electrolytic solution according to any one of claims 1 to 4, wherein the organic solvent is at least two selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, methyl formate, ethyl propionate, propyl propionate, methyl butyrate and tetrahydrofuran.
6. The nonaqueous electrolytic solution according to claim 5, wherein the organic solvent comprises ethylene carbonate, propylene carbonate, diethyl carbonate, propyl propionate, and the mass ratio of the ethylene carbonate, the propylene carbonate, the diethyl carbonate, the propyl propionate is 1:1:2:6.
7. A lithium ion battery comprising the nonaqueous electrolytic solution according to any one of claims 1 to 6.
8. The lithium ion battery of claim 7, further comprising a positive electrode sheet comprising a positive electrode current collector and a positive electrode active slurry layer on the positive electrode current collector, the positive electrode active slurry layer comprising a positive electrode active material, the positive electrode active material being one or more selected from the group consisting of lithium cobaltate, lithium nickel manganese cobalt ternary material, lithium iron phosphate, lithium manganate.
CN202310068551.0A 2023-02-06 2023-02-06 Nonaqueous electrolyte and lithium ion battery thereof Pending CN116130771A (en)

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