CN114583270A - Lithium ion battery - Google Patents
Lithium ion battery Download PDFInfo
- Publication number
- CN114583270A CN114583270A CN202210086571.6A CN202210086571A CN114583270A CN 114583270 A CN114583270 A CN 114583270A CN 202210086571 A CN202210086571 A CN 202210086571A CN 114583270 A CN114583270 A CN 114583270A
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- CN
- China
- Prior art keywords
- positive electrode
- lithium ion
- ion battery
- material layer
- compound
- Prior art date
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 61
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 59
- 239000007774 positive electrode material Substances 0.000 claims abstract description 56
- 239000007773 negative electrode material Substances 0.000 claims abstract description 33
- 239000000654 additive Substances 0.000 claims abstract description 31
- 230000000996 additive effect Effects 0.000 claims abstract description 27
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 23
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 15
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 6
- 229910032387 LiCoO2 Inorganic materials 0.000 claims abstract description 5
- -1 aliphatic carboxylate Chemical class 0.000 claims description 65
- 229910052744 lithium Inorganic materials 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 239000010405 anode material Substances 0.000 claims description 10
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- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- AHKHZLVXUVZTGF-UHFFFAOYSA-M lithium dihydrogen phosphate oxalic acid Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] AHKHZLVXUVZTGF-UHFFFAOYSA-M 0.000 description 1
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical class [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- HSAPVOPSUVJVGL-UHFFFAOYSA-N methyl bis(prop-2-ynyl) phosphate Chemical compound C#CCOP(=O)(OC)OCC#C HSAPVOPSUVJVGL-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- MRDKYAYDMCRFIT-UHFFFAOYSA-N oxalic acid;phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)C(O)=O MRDKYAYDMCRFIT-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- AIKFSRURHOARNU-UHFFFAOYSA-N propyl bis(prop-2-ynyl) phosphate Chemical compound CCCOP(=O)(OCC#C)OCC#C AIKFSRURHOARNU-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
Abstract
In order to overcome the problem of insufficient safety performance of the conventional high-voltage and high-compaction lithium ion battery, the invention provides a lithium ion battery which comprises a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein the negative electrode comprises a negative electrode material layer, the positive electrode comprises a positive electrode material layer, the positive electrode material layer comprises a positive electrode active material, and the positive electrode active material comprises LiCoO2The nonaqueous electrolytic solution comprises a nonaqueous organic solvent, a lithium salt and an additive, wherein the additive comprises a compound shown as a structural formula 1:
wherein n is 0 or 1, A is selected from C or O, X is selected from
Or
R1、R2Each independently selected from H,
Or
R1And R2Is not simultaneously selected from H, and X, R1And R2Contains at least one sulfur atom; the lithium ion battery meets the following conditions:
a is more than or equal to 8 percent and less than or equal to 58 percent, m is more than or equal to 0.05 percent and less than or equal to 5 percent, 1.55g/cm3≤n≤1.9g/cm3. The lithium ion battery provided by the invention effectively improves the safety performance of the battery.
Description
Technical Field
The invention belongs to the technical field of energy storage battery devices, and particularly relates to a lithium ion battery.
Background
The lithium ion battery has the advantages of high working voltage, wide working temperature range, high energy density and power density, no memory effect, long cycle life and the like, and is widely applied to the fields of 3C digital products such as mobile phones, notebook computers and the like and new energy automobiles. In recent years, with the development of thinning and thinning of 3C digital products, the demand of the battery industry for high energy density of lithium ion batteries is increasing, and good safety performance has become a basic demand of batteries in consideration of clients.
In the positive electrode side, LiCoO2Has the highest volume energy density among a plurality of anode materials and simultaneously has better rate performance, but LiCoO is gradually increased along with the gradual increase of the battery voltage2And when the lithium ion battery enters a higher lithium removal state, the structural stability of the material is poor, and the Co in the anode is easy to generate disproportionation reaction and is dissolved in the electrolyte in an ion form, so that the structure of the anode is damaged, and the thermal runaway risk is easy to occur at high temperature and high pressure. The dissolved Co migrates to the negative electrode interface, and undergoes ion exchange with lithium in the negative electrode, and occupies a negative electrode lithium insertion position, so that the negative electrode lithium storage capacity is reduced, and various battery performances are deteriorated, specifically: electricityThe pool generates gas, the internal resistance is rapidly increased, and the capacity is sharply reduced. The generation of gas from the battery may increase the internal pressure, which may further lead to dangerous situations such as explosion and burning of the battery, and thus the high voltage battery needs to be matched with an electrolyte with better safety performance.
The negative pole angle, for promoting energy density, high compaction has become the commonly adopted means in the industry, through the porosity that reduces the negative pole, reaches the purpose of bearing more active material. However, the higher the compaction density of the lithium ion battery negative electrode material is, the higher the requirement on the electrolyte is. The electrolyte suitable for the conventional compacted negative electrode is in a high-voltage physical system, a series of problems such as lithium precipitation, cycle life reduction, rate performance reduction and the like of the battery easily occur, and the Co ions dissolved out from the positive electrode can cause more serious damage to the negative electrode under the high-voltage actual condition, so that the risk of safety accidents of the battery is further increased.
Therefore, high voltage LiCoO is used2The design of the electrolyte is particularly important for the safety performance by matching with a battery system with a high-compaction cathode.
Disclosure of Invention
The invention provides a lithium ion battery, aiming at the problem that the safety performance of the existing high-voltage high-compaction lithium ion battery is insufficient.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a lithium ion battery, which comprises a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein the negative electrode comprises a negative electrode material layer, the positive electrode comprises a positive electrode material layer, the positive electrode material layer comprises a positive electrode active material, and the positive electrode active material comprises LiCoO2The nonaqueous electrolytic solution comprises a nonaqueous organic solvent, a lithium salt and an additive, wherein the additive comprises a compound shown as a structural formula 1:
wherein n is 0 or 1, A is selected from C or O, X is selected from
R1、R2Each independently selected from H,
R1And R2Is not simultaneously selected from H, and X, R1And R2Contains at least one sulfur atom;
the lithium ion battery meets the following conditions:
a is more than or equal to 8 percent and less than or equal to 58 percent, m is more than or equal to 0.05 percent and less than or equal to 5 percent, 1.55g/cm3≤n≤1.9g/cm3；
Wherein a is the percentage value of the mass of the non-aqueous electrolyte and the mass of the positive electrode material layer, and the unit is;
m is the mass percentage content of the compound shown in the structural formula 1 in the nonaqueous electrolyte, and the unit is;
n is the compacted density of the anode material layer and is in g/cm3。
Optionally, the lithium ion battery satisfies the following conditions:
optionally, the percentage value a of the mass of the nonaqueous electrolyte solution to the mass of the positive electrode material layer is 10% to 40%.
Optionally, the mass percentage content m of the compound shown in the structural formula 1 in the non-aqueous electrolyte is 0.05-3%.
Optionally, the compacted density n of the negative electrode material layer is 1.6g/cm3～1.85g/cm3。
Optionally, the compound shown in the structural formula 1 is selected from one or more of the following compounds 1-22:
optionally, the porosity of the negative electrode material layer is 50% or less.
Optionally, the lithium salt is selected from LiPF6、LiPO2F2、LiBF4、LiBOB、LiSbF6、LiAsF6、LiCF3SO3、LiDFOB、LiN(SO2CF3)2、LiC(SO2CF3)3、LiN(SO2C2F5)2、LiN(SO2F)2、LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiAlCl4At least one of lithium chloroborane, lithium lower aliphatic carboxylate having 4 or less carbon atoms, lithium tetraphenylborate, and lithium imide.
Optionally, the nonaqueous electrolyte further comprises an auxiliary additive, the auxiliary additive comprises at least one of a cyclic sulfate compound, a sultone compound, a cyclic carbonate compound, an unsaturated phosphate compound and a nitrile compound, and the addition amount of the auxiliary additive is 0.01-30% based on 100% of the total mass of the nonaqueous electrolyte.
Optionally, the cyclic sulfate compound is selected from at least one of vinyl sulfate, allyl sulfate or vinyl methyl sulfate;
the sultone compound is selected from at least one of 1, 3-propane sultone, 1, 4-butane sultone or 1, 3-propylene sultone;
the cyclic carbonate compound is at least one of vinylene carbonate, ethylene carbonate, fluoroethylene carbonate or a compound shown in a structural formula 2,
in the formula 2, R21、R22、R23、R24、R25、R26Each independently selected from one of hydrogen atom, halogen atom, C1-C5 group;
the unsaturated phosphate ester compound is selected from at least one of compounds shown in a structural formula 3:
in the structural formula 3, R31、R32、R32Each independently selected from saturated alkyl, unsaturated alkyl, halogenated alkyl and Si (C1-C5)mH2m+1)3M is a natural number of 1 to 3, and R31、R32、R33At least one of them is an unsaturated hydrocarbon group;
the nitrile compound is selected from one or more of succinonitrile, glutaronitrile, ethylene glycol bis (propionitrile) ether, hexanetricarbonitrile, adiponitrile, pimelonitrile, suberonitrile, nonadinitrile and sebaconitrile.
According to the lithium ion battery provided by the invention, LiCoO is adopted2As a positive electrode active material and a negative electrode material layer with high compaction density, the energy density of the battery can be effectively improved, and meanwhile, the compound shown in the formula 1 is added into the non-aqueous electrolyte as an additive, the inventor finds that when the percentage value a of the mass of the non-aqueous electrolyte to the mass of the positive electrode material layer, the mass percentage content m of the compound shown in the formula 1 in the non-aqueous electrolyte and the compaction density n of the negative electrode material layer meet the conditions through a great deal of research
During the process, the compound shown in the structural formula 1 can be decomposed at the positive and negative electrode interfaces to generate a passivation film with a more stable and more compact structure and composition, which is beneficial to reducing the dissolution of Co ions in the positive electrode, avoiding the problem of thermal runaway caused by the structural damage of the positive electrode material, simultaneously improving the stability of the negative electrode and inhibiting the increase of the impedance of the negative electrode, thereby avoiding the heat accumulation in the battery caused by too large impedance and effectively improving the safety performance of the battery.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a lithium ion battery, which comprises a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein the negative electrode comprises a negative electrode material layer, the positive electrode comprises a positive electrode material layer, the positive electrode material layer comprises a positive electrode active material, and the positive electrode active material comprises LiCoO2The nonaqueous electrolyte comprises a nonaqueous organic solvent, a lithium salt and an additive, wherein the additive comprises a compound shown in a structural formula 1:
wherein n is 0 or 1, A is selected from C or O, X is selected from
R1、R2Each independently selected from H,
R1And R2Is not simultaneously selected from H, and X, R1And R2Contains at least one sulfur atom;
the lithium ion battery meets the following conditions:
a is more than or equal to 8 percent and less than or equal to 58 percent, m is more than or equal to 0.05 percent and less than or equal to 5 percent, 1.55g/cm3≤n≤1.9g/cm3；
Wherein a is the percentage value of the mass of the non-aqueous electrolyte and the mass of the positive electrode material layer, and the unit is;
m is the mass percentage content of the compound shown in the structural formula 1 in the nonaqueous electrolyte, and the unit is;
n is the compacted density of the anode material layer and is in g/cm3。
The inventors have found, through extensive studies, that when the percentage value a of the mass of the nonaqueous electrolytic solution to the mass of the positive electrode material layer, the mass percentage content m of the compound represented by the formula 1 in the nonaqueous electrolytic solution, and the compacted density n of the negative electrode material layer satisfy the condition
During the process, the compound shown in the structural formula 1 can be decomposed at the positive and negative electrode interfaces to generate a passivation film with a more stable and more compact structure and composition, which is beneficial to reducing the dissolution of Co ions in the positive electrode, avoiding the problem of thermal runaway caused by the structural damage of the positive electrode material, simultaneously improving the stability of the negative electrode and inhibiting the increase of the impedance of the negative electrode, thereby avoiding the heat accumulation in the battery caused by too large impedance and effectively improving the safety performance of the battery.
In some embodiments, when n is 0, the compound of formula 1 is:
wherein A is selected from C or O, and X is selected from
R1、R2Each independently selected from H,
R1And R2Is not simultaneously selected from H, and X, R1And R2Contains at least one sulfur atom.
In some embodiments, when n is 1, the compound of formula 1 is:
wherein A is selected from C or O, and X is selected from
R1、R2Each independently selected from H,
R1And R2Is not simultaneously selected from H, and X, R1And R2Contains at least one sulfur atom.
In a preferred embodiment, the lithium ion battery satisfies the following condition:
the percentage value a of the mass of the non-aqueous electrolyte and the mass of the positive electrode material layer, the mass percentage content m of the compound shown in the structural formula 1 in the non-aqueous electrolyte and the compaction density n of the negative electrode material layer are correlated, so that the influences of the positive electrode, the negative electrode and the non-aqueous electrolyte on the battery performance can be integrated to a certain extent, and the lithium ion battery with excellent safety performance is obtained.
In specific examples, the percentage value a of the mass of the nonaqueous electrolytic solution to the mass of the positive electrode material layer may be 8%, 9%, 10%, 13%, 15%, 16%, 18%, 21%, 23%, 24%, 26%, 27%, 29%, 30%, 32%, 33%, 35%, 39%, 41%, 43%, 46%, 49%, 53%, 56%, or 58%.
In a preferred embodiment, the percentage value a of the mass of the nonaqueous electrolyte solution to the mass of the positive electrode material layer is 10-40%.
Because the positive electrode material layer is a porous material, the compound shown in the structural formula 1 is decomposed on the surface of the positive electrode material layer to form a passive film, the percentage value a of the quality of the non-aqueous electrolyte and the quality of the positive electrode material layer influences the infiltration of the non-aqueous electrolyte on the positive electrode material layer, and further influences the surface contact efficiency of the compound shown in the structural formula 1 in the non-aqueous electrolyte and the positive electrode material layer, and simultaneously, the percentage value a of the quality of the non-aqueous electrolyte and the quality of the positive electrode material layer also determines the total amount of the compound shown in the structural formula 1 in the battery together with the mass percentage content m of the compound shown in the structural formula 1 in the non-aqueous electrolyte, therefore, the percentage value a of the quality of the non-aqueous electrolyte and the quality of the positive electrode material layer is a limiting condition directly related to the battery system, and the percentage value a of the quality of the non-aqueous electrolyte and the positive electrode material layer is too large, so that the free non-aqueous electrolyte in the lithium ion battery is increased, the gas production probability of the battery is increased; and the percentage value a of the mass of the nonaqueous electrolyte solution to the mass of the positive electrode material layer is too small, so that the intercalation and deintercalation efficiency of lithium ions in the positive electrode material layer is influenced, the impedance of the battery is increased, meanwhile, enough compound of the structural formula 1 does not react with the positive electrode material layer to form a passivation film, and a nonaqueous organic solvent in the nonaqueous electrolyte solution participates in decomposition reaction, so that the problems of gas generation and cycle performance reduction are also caused.
In specific examples, the content m of the compound represented by structural formula 1 in the nonaqueous electrolytic solution may be 0.05%, 0.1%, 0.12%, 0.15%, 0.3%, 0.5%, 0.8%, 0.9%, 1.0%, 1.2%, 1.4%, 1.7%, 1.9%, 2.1%, 2.2%, 2.4%, 2.7%, 2.9%, 3.1%, 3.3%, 3.5%, 3.7%, 4.2%, 4.4%, 4.7%, 4.9%, or 5.0% by mass.
In a preferred embodiment, the mass percentage content m of the compound shown in the structural formula 1 in the nonaqueous electrolytic solution is 0.05-3%.
In a more preferable embodiment, the mass percentage content m of the compound represented by the formula 1 in the nonaqueous electrolytic solution is 0.1-2%.
If the content of the compound shown in the structural formula 1 in the non-aqueous electrolyte is too low, the generation quality of a passive film on the surface of a positive electrode and a negative electrode is influenced, and the Co ions in the positive electrode are difficult to effectively inhibit dissolving out and protect a negative electrode material layer; if the content of the compound represented by the formula 1 in the nonaqueous electrolyte is too large, the viscosity of the nonaqueous electrolyte increases, the wetting of the nonaqueous electrolyte with the positive and negative electrode materials is affected, and the impedance increases, so that the battery performance is affected.
In particular embodiments, the compacted density n of the anode material layer may be 1.55g/cm3、1.6g/cm3、1.65g/cm3、1.7g/cm3、1.75g/cm3、1.8g/cm3、1.83g/cm3、1.86g/cm3、1.89g/cm3Or 1.9g/cm3
In a preferred embodiment, the compacted density n of the anode material layer is 1.6g/cm3～1.85g/cm3。
In a more preferred embodiment, the compacted density n of the anode material layer is 1.65g/cm3～1.85g/cm3。
The negative electrode material layer is of a porous structure, and the charge and discharge process of the battery actually comprises liquid phase conduction of lithium ions in the negative electrode material layer, so that the electrochemical performance of the battery is directly influenced by the richness of pore channels in the negative electrode material layer. Under the same other conditions, the smaller the compaction density of the negative electrode material layer is, the more developed the pore structure is, and the more favorable the liquid phase conduction of active ions is, especially under the severe conditions that the battery undergoes repeated expansion of charge and discharge for many times. However, the compaction density is too low, so that the negative pole piece is subjected to demoulding and powder dropping, the electronic conductivity is poor during charging, lithium precipitation is generated, the electrochemical performance of the battery is influenced, and the energy density of the battery is reduced. Since the compaction density of the negative electrode influences the wetting effect of the nonaqueous electrolytic solution on the negative electrode and the volume expansion rate of the negative electrode, the compaction size is also directly related to the performance of the battery system. When the compacted density of the anode material layer is in the above range, the lithium ion battery has the best performance.
In some embodiments, the compound of formula 1 is selected from one or more of the following compounds 1-22:
it should be noted that the above are only preferred compounds of the present invention, and do not represent limitations of the present invention.
In the case where the structural formula of the compound represented by the structural formula 1 is known, those skilled in the art can know the preparation method of the compound according to the common general knowledge in the field of chemical synthesis. For example: compound 7 can be made by the following method:
putting sorbitol, dimethyl carbonate, methanol alkaline substance catalysts potassium hydroxide, DMF and other organic solvents into a reaction vessel, reacting for several hours under heating conditions, adding a certain amount of oxalic acid to adjust the pH value to be neutral, filtering, recrystallizing to obtain an intermediate product 1, carrying out esterification reaction on the intermediate product 1, carbonate, thionyl chloride and the like under a high-temperature condition to obtain an intermediate product 2, and oxidizing the intermediate product 2 by using sodium periodate and other oxidants to obtain a compound 7.
In some embodiments, the porosity of the anode material layer is 50% or less, preferably 35% or less.
In some embodiments, the lithium salt is selected from LiPF6、LiPO2F2、LiBF4、LiBOB、LiSbF6、LiAsF6、LiCF3SO3、LiDFOB、LiN(SO2CF3)2、LiC(SO2CF3)3、LiN(SO2C2F5)2、LiN(SO2F)2、LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiAlCl4At least one of lithium chloroborane, lithium lower aliphatic carboxylate having 4 or less carbon atoms, lithium tetraphenylborate, and lithium imide. Specifically, the lithium salt may be LiBF4、LiClO4、LiAlF4、LiSbF6、LiTaF6、LiWF7Inorganic lithium salts; LiPF (lithium ion particle Filter)6Lithium salts of isofluorophosphates; LiWOF5Lithium tungstate salts; HCO2Li、CH3CO2Li、CH2FCO2Li、CHF2CO2Li、CF3CO2Li、CF3CH2CO2Li、CF3CF2CO2Li、CF3CF2CF2CO2Li、CF3CF2CF2CF2CO2Lithium carboxylates such as Li; CH (CH)3SO3Lithium sulfonates such as Li; LiN (FCO)2)2、LiN(FCO)(FSO2)、LiN(FSO2)2、LiN(FSO2)(CF3SO2)、LiN(CF3SO2)2、LiN(C2F5SO2)2Lithium cyclic 1, 2-perfluoroethanedisulfonimide, lithium cyclic 1, 3-perfluoropropanedisulfonimide, LiN (CF)3SO2)(C4F9SO2) Lithium imide salts; LiC (FSO)2)3、LiC(CF3SO2)3、LiC(C2F5SO2)3And the like methyllithium salts; lithium oxalate salts such as lithium difluorooxalate borate, lithium bis (oxalate) borate, lithium tetrafluorooxalate phosphate, lithium difluorobis (oxalate) phosphate and lithium tris (oxalate) phosphate; and LiPF4(CF3)2、LiPF4(C2F5)2、LiPF4(CF3SO2)2、LiPF4(C2F5SO2)2、LiBF3CF3、LiBF3C2F5、LiBF3C3F7、LiBF2(CF3)2、LiBF2(C2F5)2、LiBF2(CF3SO2)2、LiBF2(C2F5SO2)2Fluorine-containing organic lithium salts, and the like.
In general, the lithium salt in the electrolyte is a transfer unit of lithium ions, and the concentration of the lithium salt directly affects the transfer rate of the lithium ions, which affects the potential change of the negative electrode. In the process of rapidly charging the battery, the moving speed of lithium ions needs to be improved as much as possible, the formation of lithium dendrites caused by the excessively fast decline of the negative electrode potential is prevented, potential safety hazards are brought to the battery, and the excessively fast decline of the cycle capacity of the battery can be prevented.
In a preferred embodiment, the concentration of the lithium salt in the nonaqueous electrolytic solution is 0.5 to 3.5 mol/L.
In a preferred embodiment, the total concentration of the lithium salt in the electrolyte may be 0.5mol/L to 2.0mol/L, 0.5mol/L to 0.6mol/L, 0.6mol/L to 0.7mol/L, 0.7mol/L to 0.8mol/L, 0.8mol/L to 0.9mol/L, 0.9mol/L to 1.0mol/L, 1.0mol/L to 1.1mol/L, 1.1mol/L to 1.2mol/L, 1.2mol/L to 1.3mol/L, 1.3mol/L to 1.4mol/L, 1.4mol/L to 1.5mol/L, 1.5mol/L to 1.6mol/L, 1.6mol/L to 1.7mol/L, 1.7mol/L to 1.8mol/L, 1.8mol/L to 1.9mol/L, 1.9mol/L to 1.6mol/L, 1.6mol/L to 1.7mol/L, 1.7mol/L to 1.8mol/L, and further preferably 0mol/L to 1.8mol/L, 0.7mol/L to 1.7mol/L, or 0.8mol/L to 1.5 mol/L.
In some embodiments, the nonaqueous electrolytic solution further includes an auxiliary additive, and the auxiliary additive includes at least one of a cyclic sulfate compound, a sultone compound, a cyclic carbonate compound, a phosphate compound, a borate compound, and a nitrile compound;
in a preferred embodiment, the cyclic sulfate compound is selected from at least one of vinyl sulfate, propylene sulfate or vinyl methylsulfate;
the sultone compound is at least one of methylene methane disulfonate, 1, 3-propane sultone, 1, 4-butane sultone or 1, 3-propylene sultone;
the cyclic carbonate compound is at least one of ethylene carbonate, fluoroethylene carbonate or a compound shown in a structural formula 2,
in the formula 2, R21、R22、R23、R24、R25、R26Each independently selected from one of hydrogen atom, halogen atom, C1-C5 group;
the phosphate ester compound is at least one of tris (trimethylsilane) phosphate and a compound shown in a structural formula 3:
in the formula 3, R31、R32、R32Each independently selected from saturated alkyl, unsaturated alkyl, halogenated alkyl and Si (C1-C5)mH2m+1)3M is a natural number of 1 to 3, and R31、R32、R33At least one of them is an unsaturated hydrocarbon group.
In a preferred embodiment, the unsaturated phosphate ester compound may be tris (trimethylsilane) phosphate, tripropargyl phosphate, dipropargyl methyl phosphate, dipropargyl ethyl phosphate, dipropargyl propyl phosphate, dipropargyl trifluoromethyl phosphate, dipropargyl-2, 2, 2-trifluoroethyl phosphate, dipropargyl-3, 3, 3-trifluoropropyl phosphate, dipropargyl hexafluoroisopropyl phosphate, at least one of triallyl phosphate, diallyl methyl phosphate, diallyl ethyl phosphate, diallyl propyl phosphate, diallyl trifluoromethyl phosphate, diallyl-2, 2, 2-trifluoroethyl phosphate, diallyl-3, 3, 3-trifluoropropyl phosphate, and diallyl hexafluoroisopropyl phosphate.
The borate compounds are selected from tris (trimethylsilane) borate;
the nitrile compound is selected from one or more of succinonitrile, glutaronitrile, ethylene glycol bis (propionitrile) ether, hexanetrinitrile, adiponitrile, pimelonitrile, suberonitrile, nonanedionitrile and decanedionitrile.
In other embodiments, the supplemental additives may also include other additives that improve the performance of the battery: for example, additives for improving the safety performance of the battery, such as a flame retardant additive such as fluorophosphate ester and cyclophosphazene, or an anti-overcharge additive such as tert-amylbenzene and tert-butylbenzene.
In some embodiments, the additive amount of the auxiliary additive is 0.01% to 30% based on 100% of the total mass of the nonaqueous electrolytic solution.
Unless otherwise specified, in general, the additive amount of any optional substance in the auxiliary additive in the nonaqueous electrolytic solution is 10% or less, preferably 0.1 to 5%, more preferably 0.1 to 2%. Specifically, the additive amount of any optional substance in the auxiliary additive may be 0.05%, 0.08%, 0.1%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 7.8%, 8%, 8.5%, 9%, 9.5%, 10%.
In some embodiments, when the auxiliary additive is selected from fluoroethylene carbonate, the fluoroethylene carbonate is added in an amount of 0.05% to 30% based on 100% by mass of the total mass of the nonaqueous electrolytic solution.
In some embodiments, the positive electrode further comprises a positive electrode current collector, and the positive electrode material layer covers the surface of the positive electrode current collector.
The positive electrode current collector is selected from metal materials capable of conducting electrons, preferably, the positive electrode current collector comprises one or more of Al, Ni, tin, copper and stainless steel, and in a more preferred embodiment, the positive electrode current collector is selected from aluminum foil.
In some embodiments, the positive electrode active material layer further includes a positive electrode binder and a positive electrode conductive agent, and the positive electrode active material, the positive electrode binder and the positive electrode conductive agent are blended to obtain the positive electrode material layer.
The positive binder comprises thermoplastic resins such as polyvinylidene fluoride, copolymers of vinylidene fluoride, polytetrafluoroethylene, copolymers of vinylidene fluoride and hexafluoropropylene, copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ether, copolymers of ethylene and tetrafluoroethylene, copolymers of vinylidene fluoride and trifluoroethylene, copolymers of vinylidene fluoride and trichloroethylene, copolymers of vinylidene fluoride and fluoroethylene, copolymers of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene, thermoplastic polyimide, polyethylene, polypropylene and the like; an acrylic resin; and styrene butadiene rubber.
The positive electrode conductive agent comprises one or more of conductive carbon black, conductive carbon spheres, conductive graphite, conductive carbon fibers, carbon nanotubes, graphene or reduced graphene oxide.
In some embodiments, the anode material layer includes an anode active material including one or more of a carbon-based anode, a tin-based anode, a silicon-based anode, a lithium anode. Wherein the carbon-based negative electrode can comprise graphite, hard carbon, soft carbon, graphene, mesocarbon microbeads and the like; the silicon-based negative electrode may comprise one or more of a silicon material, an oxide of silicon, a silicon-carbon composite material, and a silicon alloy material; the tin-based negative electrode may include tin, tin carbon, tin oxide, tin metal compounds; the lithium negative electrode may include metallic lithium or a lithium alloy. The lithium alloy may specifically be at least one of a lithium silicon alloy, a lithium sodium alloy, a lithium potassium alloy, a lithium aluminum alloy, a lithium tin alloy, and a lithium indium alloy.
In some embodiments, the negative electrode further comprises a negative electrode current collector, and the negative electrode material layer covers the surface of the negative electrode current collector. The material of the negative current collector may be the same as that of the positive current collector, and thus, the description thereof is omitted. In a more preferred embodiment, the negative current collector is selected from copper foil.
In some embodiments, the negative electrode material layer further includes a negative electrode binder and a negative electrode conductive agent, and the negative electrode active material, the negative electrode binder and the negative electrode conductive agent are blended to obtain the negative electrode material layer. The negative binder and the negative conductive agent may be respectively the same as the positive binder and the positive conductive agent, and are not described herein again.
In some embodiments, a separator is also included in the battery, the separator being positioned between the positive electrode and the negative electrode.
The diaphragm can be an existing conventional diaphragm, and can be a ceramic diaphragm, a polymer diaphragm, non-woven fabric, an inorganic-organic composite diaphragm and the like, including but not limited to diaphragms such as single-layer PP (polypropylene), single-layer PE (polyethylene), double-layer PP/PE, double-layer PP/PP and three-layer PP/PE/PP.
The present invention will be further illustrated by the following examples.
The following examples and comparative examples relate to compounds as shown in table 1 below:
TABLE 1
Table 2 design of parameters of examples and comparative examples
Example 1
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
1) preparation of positive pole piece
LiCoO as positive electrode active material2Dispersing conductive carbon black and a binder PVDF into a non-aqueous organic solvent NMP (N-methyl-2-pyrrolidone) to be uniformly mixed to obtain anode slurry; and uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil, drying, rolling and cutting into pieces to obtain a positive electrode piece, wherein the weight ratio of the positive electrode active material to the conductive carbon black to the binder PVDF is 96:2: 2.
2) Preparation of negative electrode plate
Dispersing graphite serving as a negative active material, a conductive agent, CMC and SBR in deionized water according to a weight ratio of 96:1:1:2, and stirring to obtain negative slurry; and uniformly coating the negative electrode slurry on a copper foil of a negative current collector, drying, rolling and cutting into pieces to obtain a negative electrode piece, wherein the compaction density of the negative electrode piece is shown in table 1.
3) Preparation of non-aqueous electrolyte
Uniformly mixing Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a weight ratio of 30:70, and adding LiPF6And adding the compound shown in the formula 1 to 1mol/L, and dissolving the compound in the non-aqueous organic solvent to obtain the non-aqueous electrolyte, wherein the content of the compound shown in the formula 1 in the non-aqueous electrolyte is shown in the table 1, and the content is calculated according to the percentage of the total mass of the non-aqueous electrolyte.
4) Preparation of lithium ion battery
And (3) sequentially laminating the positive pole piece, the isolating membrane and the negative pole piece by adopting a lamination process, and then carrying out processes of top side sealing, non-aqueous electrolyte injection and the like to prepare the soft package battery. The amount of nonaqueous electrolyte injected is shown in table 1.
5) Formation of
The method comprises the following steps: charging at 0.05C for 180min, charging at 0.1C for 180min, standing for 24hr, shaping, sealing, further charging at 0.2C for stopping voltage, standing for 24hr, and discharging at 0.2C for 3.0V.
Examples 2 to 37
Examples 2 to 37 are provided to illustrate the lithium ion battery and the preparation method thereof disclosed in the present invention, and include most of the operation steps in example 1, except that:
the negative electrode compacted density, the electrolyte additive components and the electrolyte injection ratio shown in table 1 were used.
Comparative examples 1 to 15
Comparative examples 1 to 15 are provided for comparative purposes to illustrate the battery and the method for manufacturing the same disclosed in the present invention, including most of the steps of example 1, except that:
the negative electrode compacted density, the electrolyte additive components and the electrolyte injection ratio shown in table 1 were used.
Performance test
The lithium ion battery prepared above was subjected to the following performance tests:
(1) thermal shock test
And (3) standing the lithium ion battery for 5 minutes at 25 ℃, carrying out constant current charging to 4.48V at a rate of 1C, carrying out constant voltage charging until the current is less than or equal to 0.05C, and standing for 5 minutes. Then the cell was placed in a high temperature cabinet, the temperature of which was set to rise from 25 ℃ to 130 ℃ at a rate of 2 ℃/min and held for 1 hour. And monitoring the surface temperature and the state of the battery in the temperature rising process and the heat preservation process.
(2) High temperature cycle performance test
At the temperature of 45 ℃, the lithium ion secondary battery is placed aside for 5 minutes, the constant current charging is carried out to 4.48V at the rate of 1C, then the constant voltage charging is carried out until the current is less than or equal to 0.05C, then the lithium ion secondary battery is placed aside for 5 minutes, then the constant current discharging is carried out to 3.0V at the rate of 1C, 700 cycles of charge-discharge testing is carried out according to the method, the discharge capacity of each cycle is recorded, and the DCIR is discharged, so that the calculation method of the capacity retention rate and the DCIR growth rate of 700 cycles of the cycle is as follows:
the capacity retention (%) after 700 cycles was equal to the discharge capacity at 700 cycles/discharge capacity at 1 cycle × 100%.
The DCIR increase rate (%) after 700 cycles was (discharge DCIR at 700 th cycle — discharge DCIR at 1 st cycle)/discharge DCIR at 1 st cycle.
(1) The test results obtained in examples 1 to 28 and comparative examples 1 to 15 are filled in Table 3.
TABLE 3
From the test results of examples 1 to 28 and comparative examples 1 to 15, it can be seen that the percentage value a of the mass of the nonaqueous electrolytic solution to the mass of the positive electrode material layer, the mass percentage content m of the compound represented by the formula 1 in the nonaqueous electrolytic solution, and the compacted density n of the negative electrode material layer have a correlation effect with each other in the lithium ion battery, and when the percentage value a of the mass of the nonaqueous electrolytic solution to the mass of the positive electrode material layer, the mass percentage content m of the compound represented by the formula 1 in the nonaqueous electrolytic solution, and the compacted density n of the negative electrode material layer satisfy the relational expression
A is more than or equal to 8 percent and less than or equal to 58 percent, m is more than or equal to 0.05 percent and less than or equal to 5 percent, 1.55g/cm3≤n≤1.9g/cm3The obtained lithium ion battery has greatly improved thermal shock resistance and high-temperature cycle performance, and presumably because the compound shown in the structural formula 1 can generate a relatively stable and compact passive film at high temperature on the positive and negative electrode interfaces under the conditions of the addition proportion and the negative electrode compaction density, the dissolution of Co ions in a positive electrode is reduced, the stability of a positive electrode material is improved, the problem of thermal runaway caused by the structural damage of the positive electrode material is avoided, the increase of the impedance of the negative electrode is also inhibited, the heat accumulation in the battery caused by too large impedance is avoided, the surface temperature of the battery is reduced in a thermal shock state, and the safety performance and the high-temperature cycle performance of the battery are improved.
As can be seen from the test results of comparative examples 1 to 8, even the value of aThe m value and the n value meet the parameter range limitation, but when the am/n value is too large or too small, the safety performance and the high-temperature cycle performance of the battery are reduced, which shows that the percentage value a of the quality of the non-aqueous electrolyte and the quality of the positive electrode material layer, the mass percentage content m of the compound shown in the structural formula 1 in the non-aqueous electrolyte and the compaction density n of the negative electrode material layer in the lithium ion battery are mutually influenced in the aspect of improving the safety performance and the high-temperature cycle performance of the battery, and when and only when the three reach a better balance state, the electrochemical performance of the battery under the high-temperature condition can be obviously improved. Meanwhile, as can be seen from the test results of comparative examples 10 to 15, when one of the a value, the m value and the n value exceeds the defined range, even if the relationship:
the requirement (2) indicates that when the percentage value a of the quality of the non-aqueous electrolyte to the quality of the positive electrode material layer, the mass percentage content m of the compound shown in the structural formula 1 in the non-aqueous electrolyte and the compaction density n of the negative electrode material layer are too high or too low, the formation of passive films on the surfaces of a positive electrode and a negative electrode and the stability of the performance of the battery under the high-temperature condition are influenced, for example, in comparative example 11, the content of the non-aqueous electrolyte is too high, so that the viscosity of the non-aqueous electrolyte is increased, the wetting effect of the non-aqueous electrolyte on the positive electrode or the negative electrode is influenced, and the cycle performance of the lithium ion battery is influenced; in comparative example 12, if the percentage of the mass of the nonaqueous electrolyte solution to the mass of the positive electrode material layer is too low, the nonaqueous electrolyte solution is not favorable for wetting the positive electrode material layer, which results in an increase in impedance; in comparative example 13, if the percentage of the mass of the non-aqueous electrolyte to the mass of the positive electrode material layer is too high, the amount of free non-aqueous electrolyte in the lithium ion battery is too large, and the risk of gas generation and decomposition of the non-aqueous electrolyte is likely to occur at high temperature, and it can be seen from comparative example 14 and comparative example 15 that the compacted density of the negative electrode material layer is too low, the negative electrode is likely to fall off during the cycle process, and if the compacted density of the negative electrode material layer is too high, the non-aqueous electrolyte is difficult to enter the negative electrode material layer, and the cycle performance of the battery at high temperature is affected。
As can be seen from the test results of examples 1 to 28, when the relationship satisfies
And when the lithium ion battery is used, the lithium ion battery has the best comprehensive battery performance. For example, it can be seen from the test results of examples 8, 9, 17 and 18 that when the compacted density of the negative electrode material layer and the addition amount of the compound represented by formula 1 in the nonaqueous electrolytic solution are consistent, the lithium ion battery has better safety and cycle performance when the am/n value is in the preferred range, and when the am/n value is out of the preferred range, the lithium ion battery has too much free nonaqueous electrolytic solution, and the safety and cycle performance of the battery are reduced.
From the test results of the embodiments 1 to 7 and the embodiments 14 to 19, it can be seen that, in the lithium ion battery provided by the present invention, as the addition amount of the compound represented by the structural formula 1 increases, the capacity retention rate of the lithium ion battery under a high temperature condition gradually increases, and the impedance growth rate decreases, which indicates that the compound represented by the structural formula 1 is beneficial to improving the density of the passive film on the surface of the positive electrode and the negative electrode, and when the content of the compound represented by the structural formula 1 is too high, the cycle performance of the lithium ion battery decreases under the high temperature condition, which indicates that the compound represented by the structural formula 1 added in an excessive amount increases the thickness of the passive film on the surface of the positive electrode and the negative electrode, thereby affecting the migration efficiency of lithium ions, but not facilitating the increase of the capacity retention rate under the high temperature cycle.
(2) The test results obtained in example 9 and examples 29 to 33 are filled in Table 4.
TABLE 4
From the test results of example 9 and examples 29 to 33, it is understood that the relational expressions are also satisfied when different compounds represented by the structural formula 1 are used as additives for nonaqueous electrolytic solutions
The limitation shows that the cyclic sulfur-containing groups commonly contained in the compounds shown in different structural formulas 1 play a decisive role in participating in the formation process of the passive films on the surfaces of the anode and the cathode, the S-rich passive films generated by decomposition can effectively inhibit the dissolution of Co ions, and a better protection effect is formed on the negative electrode material layer.
(3) The test results obtained in example 9 and examples 34 to 37 are shown in Table 5.
TABLE 5
From the test results of example 9 and examples 34 to 37, it is presumed that, in the battery provided by the present invention, PS (1, 3-propane sultone), DTD (vinyl sulfate), tripropargyl phosphate, or succinonitrile is added as an auxiliary additive, which can further improve the capacity retention performance of the battery and reduce the impedance increase of the battery, and that a certain co-decomposition reaction occurs between the compound represented by the structural formula 1 and the added PS (1, 3-propane sultone), DTD (vinyl sulfate), tripropargyl phosphate, and succinonitrile, which can participate in the formation of the passivation film on the surface of the electrode together, and the obtained passivation film can improve the stability of the nonaqueous electrolyte and maintain the high-temperature stability and safety performance of the battery cycle.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A lithium ion battery is characterized by comprising a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein the negative electrode comprises a negative electrode material layer, the positive electrode comprises a positive electrode material layer, the positive electrode material layer comprises a positive electrode active material, and the positive electrode active material comprises LiCoO2The nonaqueous electrolyte comprises a nonaqueous organic solvent, a lithium salt and an additive, wherein the additive comprises a compound shown in a structural formula 1:
wherein n is 0 or 1, A is selected from C or O, X is selected from
R1、R2Each independently selected from
R1And R2Is not simultaneously selected from H, and X, R1And R2Contains at least one sulfur atom;
the lithium ion battery meets the following conditions:
a is more than or equal to 8 percent and less than or equal to 58 percent, m is more than or equal to 0.05 percent and less than or equal to 5 percent, 1.55g/cm3≤n≤1.9g/cm3；
Wherein a is the percentage value of the mass of the non-aqueous electrolyte and the mass of the positive electrode material layer, and the unit is;
m is the mass percentage content of the compound shown in the structural formula 1 in the nonaqueous electrolyte, and the unit is;
n is the compacted density of the anode material layer and is in g/cm3。
2. The lithium ion battery according to claim 1, wherein the lithium ion battery satisfies the following condition:
3. the lithium ion battery according to claim 1, wherein the percentage value a of the mass of the nonaqueous electrolyte solution to the mass of the positive electrode material layer is 10% to 40%.
4. The lithium ion battery of claim 1, wherein the mass percentage m of the compound represented by the formula 1 in the nonaqueous electrolytic solution is 0.05 to 3%.
5. The lithium ion battery of claim 1, wherein the negative electrode material layer has a compacted density n of 1.6g/cm3～1.85g/cm3。
6. The lithium ion battery of claim 1, wherein the compound represented by the structural formula 1 is one or more selected from the following compounds 1 to 22:
7. the lithium ion battery according to claim 1, wherein the negative electrode material layer has a porosity of 50% or less.
8. The lithium ion battery of claim 1, wherein the lithium ion battery is characterized byThe lithium salt is selected from LiPF6、LiPO2F2、LiBF4、LiBOB、LiSbF6、LiAsF6、LiCF3SO3、LiDFOB、LiN(SO2CF3)2、LiC(SO2CF3)3、LiN(SO2C2F5)2、LiN(SO2F)2、LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiAlCl4At least one of lithium chloroborane, lithium lower aliphatic carboxylate having 4 or less carbon atoms, lithium tetraphenylborate, and lithium imide.
9. The lithium ion battery according to claim 1, further comprising an auxiliary additive in the nonaqueous electrolytic solution, wherein the auxiliary additive comprises at least one of a cyclic sulfate compound, a sultone compound, a cyclic carbonate compound, an unsaturated phosphate compound, and a nitrile compound; the addition amount of the auxiliary additive is 0.01-30% based on the total mass of the nonaqueous electrolyte solution as 100%.
10. The lithium ion battery according to claim 9, wherein the cyclic sulfate compound is selected from at least one of vinyl sulfate, propylene sulfate, or vinyl methylsulfate;
the sultone compound is selected from at least one of 1, 3-propane sultone, 1, 4-butane sultone or 1, 3-propylene sultone;
the cyclic carbonate compound is at least one of vinylene carbonate, ethylene carbonate, fluoroethylene carbonate or a compound shown in a structural formula 2,
in the formula 2, R21、R22、R23、R24、R25、R26Each independently selected from one of hydrogen atom, halogen atom, C1-C5 group;
the unsaturated phosphate ester compound is selected from at least one of compounds shown in a structural formula 3:
in the formula 3, R31、R32、R32Each independently selected from saturated alkyl, unsaturated alkyl, halogenated alkyl and Si (C1-C5)mH2m+1)3M is a natural number of 1 to 3, and R31、R32、R33At least one of them is an unsaturated hydrocarbon group;
the nitrile compound is selected from one or more of succinonitrile, glutaronitrile, ethylene glycol bis (propionitrile) ether, hexanetricarbonitrile, adiponitrile, pimelonitrile, suberonitrile, nonadinitrile and sebaconitrile.
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| WO2024032173A1 (en) * | 2022-08-09 | 2024-02-15 | 深圳新宙邦科技股份有限公司 | Lithium-ion battery |
| CN115064770A (en) * | 2022-08-18 | 2022-09-16 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
| WO2024037187A1 (en) * | 2022-08-18 | 2024-02-22 | 深圳新宙邦科技股份有限公司 | Lithium-ion battery |
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| Publication number | Publication date |
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| CN114583270B (en) | 2023-12-15 |
| WO2023142693A1 (en) | 2023-08-03 |
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