CN115513467A - Organic lithium salt lithium supplement material and lithium ion battery - Google Patents
Organic lithium salt lithium supplement material and lithium ion battery Download PDFInfo
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- CN115513467A CN115513467A CN202211372137.0A CN202211372137A CN115513467A CN 115513467 A CN115513467 A CN 115513467A CN 202211372137 A CN202211372137 A CN 202211372137A CN 115513467 A CN115513467 A CN 115513467A
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- 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
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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
- H01M10/42—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention provides a cyanophosphate additive which has a structure shown in a formula (I). The positive electrode lithium supplement material contains cyano functional groups, and can be complexed with metal ions to inhibit the diffusion of the metal ions to electrolyte, so that the catalytic reaction of the metal ions to an organic solvent is reduced, the gas production is reduced, and the high-temperature cycle performance is improved. Meanwhile, the presence of the positive electrode additive can improve the appearance and the components of the CEI film, and promote and participate in the component Li x PO y F z The formation of (2) reduces the film resistance, reduces the polarization, reduces the consumption of lithium ions, and improves the efficiency. And the positive electrode lithium supplement additive is insensitive to moisture, has excellent stability in air, can reduce the requirement on the environment in the preparation process of the positive electrode plate, and is a positive electrode lithium supplement agent with great potential.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode lithium supplement materials, relates to a cyanophosphate additive and a lithium ion battery, and particularly relates to an organic lithium salt lithium supplement material and a lithium ion battery.
Background
Lithium ion batteries are favored by various countries because of their advantages of high energy density, low self-discharge rate, long cycle life, cleanliness and no pollution. Electronic mobile devices such as notebook computers, mobile phones, handheld game consoles and tablet computers can realize more and more functions, and application technologies in the aspects of electric vehicles, smart grids and the like are becoming mature. Meanwhile, consumers also put higher requirements on mutual consideration of energy density, cycle life and environmental suitability of the battery.
In order to increase the energy density of lithium ion batteries, the industry needs to develop higher-performance electrode materials, so as to improve the performance of lithium ion batteries. The energy density and cycle life of a lithium ion battery are closely related to the formation of a negative electrode Solid Electrolyte Interface (SEI) film, and during the first charging process of the lithium ion battery, the SEI film formed on the surface of the negative electrode converts a large amount of active lithium into lithium carbonate, lithium fluoride and alkyl lithium, thereby causing lithium loss of the positive electrode material. In a lithium ion battery system using graphite as the negative electrode, about 10% of the lithium source is consumed for the first charge; when a material having a high specific capacity such as an alloy (silicon, tin, or the like) or an oxide (silicon oxide, tin oxide), is used as the negative electrode, the consumption of the positive electrode lithium source is further increased.
The current solution to this problem is to supplement the lithium loss during the cycling process by a lithium supplement technique. The lithium supplement technology mainly comprisesAnd lithium is supplemented to the negative electrode and lithium is supplemented to the positive electrode, wherein the lithium is supplemented to the negative electrode mainly by a metal lithium supplementing mode or a material end chemical lithium supplementing mode at a pole piece end. Lithium is supplemented to the negative electrode at the end of the pole piece, the use of combustible and explosive metal lithium is involved, the safety risk is higher, the chemical lithium supplementing process at the end of the material is complex, the alkalinity of the material is stronger, and the processing of the material is difficult. Compared with the negative pole lithium supplement, the positive pole lithium supplement process is simple, and the lithium source is added in the positive pole slurry stirring process, so that the safety risk and the cost increase risk in the negative pole end lithium supplement can be completely avoided. However, existing positive electrode lithium supplementing materials (e.g., lithium L-ascorbate, lithium D-erythorbate, lithium metabisulfite, lithium sulfite, lithium phytate, li) 5 FeO 4 、Li 2 NiO 2 Etc.) are sensitive to humidity, are easily oxidized in the air, are difficult to synthesize in large quantities, and are not beneficial to large-scale industrial production.
Therefore, how to find a more suitable positive electrode lithium supplement additive with excellent comprehensive performance to solve the above problems of the existing positive electrode lithium supplement materials becomes one of the problems to be solved urgently by a plurality of front-line researchers and scientific research enterprises in the field.
Disclosure of Invention
In view of the above, the present invention provides a cyanophosphate additive and a lithium ion battery. The cyanophosphate additive provided by the invention is an organic lithium salt lithium supplement material of the lithium ion battery anode, has the advantages of low gas production rate, good stability and long cycle life, and can well improve the lithium ion conductivity.
The invention provides a cyanophosphate additive, which has a structure shown in a formula (I):
wherein, R is 1 Selected from cyano-containing groups;
the R is 2 Selected from lithium ion, C1-C6 saturated hydrocarbon group, C1-C6 unsaturated hydrocarbon group, alkoxy, cyanoalkyl, halogenated alkyl, phenyl, silyl or substitutedA silane group of (a).
Preferably, the cyano-containing group includes a cyanoalkyl group or a substituted cyanoalkyl group;
the substitution includes halogen substitution;
the cyano phosphate additive is a positive electrode additive;
the positive electrode comprises a lithium ion battery positive electrode.
Preferably, the cyanophosphate ester additive has a structure represented by any one of formulas (1) to (11):
preferably, the cyanophosphate additive is a positive electrode organic lithium salt lithium supplement material;
the mass ratio of the cyanophosphate additive to the positive active material is (0.5-5): (75-97.5);
the cyanophosphate additive is a positive electrode additive for improving the appearance and/or components of the CEI film;
the cyanophosphate additive promotes and participates in the component Li x PO y F z Is performed.
The invention provides a lithium ion battery, which comprises a positive electrode, a negative electrode and electrolyte;
the positive electrode comprises the cyanophosphate additive described in any one of the above technical schemes.
Preferably, the positive electrode further comprises a positive electrode active material, a positive electrode conductive agent and a positive electrode binder;
the positive active material comprises one or more of lithium cobaltate, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, lithium vanadate, lithium manganate, lithium nickelate, lithium nickel cobalt manganese oxide, a lithium-rich manganese-based material, lithium nickel cobalt aluminate and lithium titanate;
the positive electrode conductive agent comprises one or more of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene and carbon nanotubes;
the positive binder comprises one or more of polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene and polyhexafluoropropylene;
the preparation process of the positive electrode comprises the steps of uniformly mixing the cyanophosphate additive, the positive electrode active material, the positive electrode conductive agent, the positive electrode binder and the solvent in the positive electrode pulping process, and then coating, rolling and drying to obtain the positive electrode sheet.
Preferably, the mass content of the positive electrode active material in the positive electrode is 75-97.5% by taking the cyanophosphate additive, the positive electrode active material, the positive electrode conductive agent and the positive electrode binder as a whole;
the anode is integrally calculated by using a cyano phosphate additive, an anode active material, an anode conductive agent and an anode binder, and the mass content of the anode conductive agent is 1-10%;
the anode is integrally calculated by using a cyano phosphate additive, an anode active material, an anode conductive agent and an anode binder, and the mass content of the anode binder is 1-10%;
the anode is integrally calculated by using a cyanophosphate additive, an anode active material, an anode conductive agent and an anode binder, and the mass content of the cyanophosphate additive is 0.5-5%.
Preferably, the negative electrode includes a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder;
the negative active material comprises graphite and/or a silicon-based material;
the negative electrode conductive agent comprises one or more of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene and carbon nanotubes;
the negative electrode binder comprises one or more of polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene and polyhexafluoropropylene.
Preferably, the electrolyte comprises a solvent;
the solvent comprises one or more of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, dimethyl ether, diethyl ether, adiponitrile, succinonitrile, glutaronitrile, dimethyl sulfoxide, sulfolane, 1,4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate, butyl propionate and ethyl butyrate;
the mass content of the solvent in the electrolyte is 50-98%;
the electrolyte includes a lithium salt;
the lithium salt comprises one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate and lithium bis-fluorosulfonyl imide;
the mass content of the lithium salt in the electrolyte is 1-18%.
Preferably, the electrolyte comprises a first auxiliary additive;
the first auxiliary additive comprises one or more of 1,3-propane sultone, 1,4-butane sultone, propenyl-1,3-sultone, vinyl sulfate, propylene sulfate, butylene sulfite, vinylene carbonate and fluoroethylene carbonate;
the mass content of the first auxiliary additive in the electrolyte is 0.1-3.0%;
the electrolyte comprises a second auxiliary additive;
the second auxiliary additive comprises one or more of lithium bis-fluorosulfonyl imide, lithium difluorooxalato borate, lithium difluorooxalato phosphate, lithium difluorophosphate and lithium tetrafluoroborate;
the molar content of the second auxiliary additive in the electrolyte is 0.001-1.0M.
The invention provides a cyanophosphate additive which has a structure shown in a formula (I). Compared with the prior art, the invention is based on the problems of the prior positive electrode lithium supplement agent, and researches show that the prior lithium supplement agent can generate gases such as carbon dioxide and the like in the decomposition process to influence the cycle life, and secondly, the lithium supplement agent does not contain a group capable of capturing metal lithium ions, can not uniformly dissolve the metal ions, does not contain a P-containing group, forms an interface film, has larger impedance and the like.
The invention particularly designs a cyanophosphate additive with a specific structure and composition, which is an organic lithium salt lithium supplement material. The anode lithium supplement material contains a cyano functional group, and can be complexed with metal ions so as to inhibit the diffusion of the metal ions to electrolyte, further reduce the catalytic reaction of the metal ions to an organic solvent, reduce the gas production and improve the high-temperature cycle performance. Meanwhile, the presence of the positive electrode additive can improve the appearance and the components of the CEI film, and promote and participate in the component Li x PO y F z The film resistance is reduced, the polarization is reduced, the consumption of lithium ions is reduced, and the efficiency is improved. And the positive electrode lithium supplement additive is insensitive to moisture, has excellent stability in air, can reduce the requirement on the environment in the preparation process of the positive electrode plate, and is a positive electrode lithium supplement agent with great potential.
The organic lithium phosphate compound containing the cyano group provided by the invention is used as a lithium supplement material, and can be complexed with metal ions from the aspect of performance so as to inhibit the diffusion of the metal ions to an electrolyte, further reduce the catalytic reaction of the metal ions to an organic solvent, reduce the gas production and improve the high-temperature cycle performance; and the lithium supplement agent contains phosphate groups, the existence of the structure improves the appearance and the components of the CEI film, and promotes and participates in the component Li x PO y F z The formation of the phosphate ester group reduces the film impedance, reduces the polarization, reduces the consumption of lithium ions, improves the efficiency, ensures that the phosphate ester group is less prone to generate gas compared with a carbonate lithium supplement agent, has flame retardant property and improves the safety of the battery; meanwhile, the lithium supplement agent can also introduce corresponding groups according to the needs to match the needs of practical application; in addition, the lithium supplement agent is not sensitive to moisture and oxygen, so that a battery prepared by using the lithium supplement agent does not need a special environment.
The positive electrode lithium supplement agent provided by the invention has the advantages of low gas production, good stability and long cycle life, can well improve the conductivity of lithium ions, is a positive electrode lithium supplement additive with excellent comprehensive performance, and can be used for reducing the gas production and improving the stability, energy density and high-temperature storage performance of lithium ion batteries.
Experimental results show that the existence of cyano functional groups in the positive organic lithium salt lithium supplement agent provided by the invention can prolong the cycle life of the battery and reduce the gas yield; the lithium supplement additive contains F, so that the internal resistance of the battery can be reduced, and the cycle life, high-temperature storage and other performances of the battery can be improved by using the additive.
Drawings
FIG. 1 is an infrared spectrum of a cyanophosphate ester additive having the structure of formula (1) prepared by the present invention;
FIG. 2 is a nuclear magnetic H spectrum of a cyanophosphate ester additive with a structure of formula (1) prepared by the present invention;
FIG. 3 is a graph comparing the capacity retention rates of example 1 of the present invention and comparative example 1;
fig. 4 is a boxplot of the first efficiencies of example 1, comparative example 1, example 4, and comparative example 2 of the present invention.
Detailed Description
In order to further understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the invention are not particularly limited in purity, and the invention preferably adopts analytically pure or purity conventional in the field of lithium ion battery anode materials.
The invention provides a cyanophosphate additive, which has a structure shown in a formula (I):
wherein, R is 1 Selected from cyano-containing groups;
said R is 2 Selected from lithium ions, saturated hydrocarbon groups of C1-C6, unsaturated hydrocarbon groups of C1-C6, alkoxy, cyanoalkyl, halogenated alkyl, phenyl or silyl or substituted silyl.
In the present invention, the C1 to C6 saturated hydrocarbon group may be a C2 to C5 saturated hydrocarbon group or a C3 to C4 saturated hydrocarbon group. The unsaturated hydrocarbon group having 1 to 6 carbon atoms may be an unsaturated hydrocarbon group having 2 to 5 carbon atoms or an unsaturated hydrocarbon group having 3 to 4 carbon atoms.
In the present invention, the substituted silane group may specifically be a halogenated silane group.
In the present invention, the cyano-containing group preferably includes a cyanoalkyl group or a substituted cyanoalkyl group.
In the present invention, the substitution preferably includes halogen substitution.
In the present invention, the term "hydrocarbyl" encompasses alkyl, alkenyl, alkynyl.
In the present invention, the term "alkyl" encompasses straight-chain and branched alkyl groups including, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl and the like. In addition, the alkyl group may be optionally substituted.
In the present invention, the term "alkenyl" encompasses straight-chain and branched alkenyl groups. For example, the alkenyl group may be C 2 -C 50 Alkenyl radical, C 2 -C 40 Alkenyl radical, C 2 -C 30 Alkenyl radical, C 2 -C 20 Alkenyl radical, C 2 -C 12 Alkenyl radical, C 2 -C 10 Alkenyl radical, C 2 -C 6 An alkenyl group. In addition, the alkenyl group may be optionally substituted.
In the present invention, the cyanophosphate ester additive is preferably a positive electrode additive.
In the present invention, the positive electrode preferably includes a lithium ion battery positive electrode.
In the present invention, the cyanophosphate ester additive preferably has a structure represented by any one of the formulae (1) to (11):
in the invention, the cyanophosphate additive is preferably a positive organic lithium salt lithium supplement material.
In the present invention, the mass ratio of the cyanophosphate ester additive to the positive electrode active material is preferably (0.5 to 5): (75 to 97.5), more preferably (1 to 4): (75-97.5), more preferably (2-3): (75-97.5), more preferably (0.5-5): (80-92), more preferably (0.5-5): (85 to 87).
In the present invention, the cyanophosphate ester additive is preferably a positive electrode additive for improving the morphology and/or composition of the CEI film, and more preferably a positive electrode additive for improving the morphology or composition of the CEI film.
In the present invention, the cyanophosphate ester additive preferably promotes and participates in the component Li x PO y F z Is performed.
The invention is a complete and refined integral technical scheme, better ensures the lithium supplementing effect of the anode lithium supplementing agent, further reduces the gas production rate, improves the stability and the cycle life of the lithium ion battery, and improves the conductivity of the lithium ion, and the cyanophosphate additive preferably comprises the following structures and compositions:
the organic lithium salt lithium supplement material is characterized in that: the organic lithium salt additive is a cyano phosphate additive. The structure is as follows:
R 1 represents a cyano-containing group, R 2 Represents lithium ions or saturated or unsaturated hydrocarbon groups having 1 to 6 carbon atoms, alkoxy groups, cyano-substituted alkyl groups, haloalkyl groups, phenyl groups, silyl groups or substituted silyl groups.
Wherein the hydrocarbyl group comprises alkyl, alkenyl and alkynyl;
alkyl encompasses straight and branched chain alkyl groups including, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl and the like. In addition, the alkyl group may be optionally substituted.
Alkenyl encompasses straight-chain and branched alkenyl. For example, the alkenyl group may be a C2-C50 alkenyl group, a C2-C40 alkenyl group, a C2-C30 alkenyl group, a C2-C20 alkenyl group, a C2-C12 alkenyl group, a C2-C10 alkenyl group, a C2-C6 alkenyl group. In addition, the alkenyl group may be optionally substituted.
The substituted silane group may be a halogen substituted silane group.
The additive includes, but is not limited to, the following structures in the following formulas (1) to (11), and may be represented by formulas (1) to (11)
Taking one of the above structures as an example, the preparation method of the positive electrode lithium supplement material of the present invention is described as follows:
(1) Taking 3-hydroxypropionitrile and phosphorus oxyhalide as raw materials, adding a halogen chelating agent, and reacting for a certain time in an organic solvent environment such as n-hexane and the like;
(2) Extracting the solution after the reaction by using dichloromethane, and distilling the filtrate under reduced pressure to obtain a reaction intermediate crude product;
(3) Adding the crude reaction intermediate into ice water to dissolve, adding dichloroethane to fully dissolve stirring, separating with a separating funnel to obtain water phase (the product is extracted into the water phase);
(4) Adding Li to the aqueous phase obtained in (3) 2 CO 3 Controlling the pH value to be 6-9 to obtain a lithium cyanophosphate mixed solution;
(5) And (3) distilling the solution containing the lithium cyanophosphate under reduced pressure to remove the solvent, and then washing, centrifuging and drying the solution for multiple times by using methanol to obtain the product.
Referring to fig. 1, fig. 1 is an infrared spectrum of a cyanophosphate ester additive having a structure of formula (1) prepared according to the present invention;
referring to fig. 2, fig. 2 is a nuclear magnetic H spectrum of the cyanophosphate additive with the structure of formula (1) prepared by the present invention.
The invention provides a lithium ion battery, which comprises a positive electrode, a negative electrode and electrolyte;
in the present invention, the positive electrode preferably includes the cyanophosphate additive according to any one of the above-described embodiments.
In the present invention, the positive electrode further preferably includes a positive electrode active material, a positive electrode conductive agent, and a positive electrode binder
In the present invention, the positive active material preferably includes one or more of lithium cobaltate, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, sodium vanadyl phosphate, lithium vanadate, lithium manganate, lithium nickelate, lithium nickel cobalt manganese manganate, a lithium rich manganese-based material, lithium nickel cobalt aluminate, and lithium titanate, and more preferably lithium cobaltate, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, sodium vanadyl phosphate, lithium vanadate, lithium manganate, lithium nickelate, lithium nickel cobalt manganate, a lithium rich manganese-based material, lithium nickel cobalt aluminate, or lithium titanate.
In the present invention, the positive electrode conductive agent preferably includes one or more of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene, and carbon nanotubes, and more preferably conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene, or carbon nanotubes.
In the present invention, the positive electrode binder preferably includes one or more of polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene, and polyhexafluoropropylene, and more preferably polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene, or polyhexafluoropropylene.
In the invention, the preparation process of the positive electrode preferably comprises the steps of uniformly mixing the cyanophosphate additive, the positive active material, the positive conductive agent, the positive adhesive and the solvent in the positive electrode pulping process, and then coating, rolling and drying to obtain the positive electrode piece.
In the present invention, the mass content of the positive electrode active material in the positive electrode is preferably 75% to 97.5%, more preferably 80% to 92%, and even more preferably 85% to 87%, based on the entirety of the cyanophosphate additive, the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder.
In the present invention, the positive electrode contains the cyanophosphate additive, the positive electrode active material, the positive electrode conductive agent and the positive electrode binder in an amount of preferably 1% to 10%, more preferably 3% to 8%, and still more preferably 5% to 6% by mass, based on the total amount of the positive electrode.
In the invention, the mass content of the positive electrode binder is selected from 1% to 10%, more preferably from 3% to 8%, and more preferably from 5% to 6%, based on the total amount of the cyanophosphate additive, the positive electrode active material, the positive electrode conductive agent and the positive electrode binder.
In the present invention, the mass content of the cyanophosphate additive in the positive electrode is preferably 0.5% to 5%, more preferably 1% to 4%, and still more preferably 2% to 3%, based on the entirety of the cyanophosphate additive, the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder.
In the present invention, the anode preferably includes an anode active material, an anode conductive agent, and an anode binder.
In the present invention, the negative active material preferably includes graphite and/or a silicon-based material, and more preferably graphite or a silicon-based material.
In the present invention, the negative electrode conductive agent preferably includes one or more of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene, and carbon nanotubes, and more preferably conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene, or carbon nanotubes.
In the present invention, the negative electrode binder preferably includes one or more of polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene, and polyhexafluoropropylene, and more preferably polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene, or polyhexafluoropropylene.
In the present invention, the electrolyte preferably includes a solvent.
In the present invention, the solvent preferably includes one or more of ethylene carbonate, propylene carbonate, methylethyl carbonate, dimethyl carbonate, diethyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, dimethyl ether, diethyl ether, adiponitrile, succinonitrile, glutaronitrile, dimethyl sulfoxide, sulfolane, 1,4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate, butyl propionate and ethyl butyrate, and more preferably ethylene carbonate, propylene carbonate, methylethyl carbonate, dimethyl carbonate, diethyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, dimethyl ether, diethyl ether, adiponitrile, succinonitrile, glutaronitrile, dimethyl sulfoxide, sulfolane, 1,4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate, butyl propionate or ethyl butyrate.
In the present invention, the mass content of the solvent in the electrolyte solution is preferably 50% to 98%, more preferably 60% to 88%, and still more preferably 70% to 78%.
In the present invention, the electrolyte preferably includes a lithium salt.
In the present invention, the lithium salt preferably includes one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate and lithium bis fluorosulfonylimide, and more preferably lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate or lithium bis fluorosulfonylimide.
In the present invention, the mass content of the lithium salt in the electrolyte solution is preferably 1% to 18%, more preferably 4% to 15%, and still more preferably 7% to 12%.
In the present invention, the electrolyte preferably includes a first auxiliary additive.
In the present invention, the first auxiliary additive preferably includes one or more of 1,3-propane sultone, 1,4-butane sultone, propenyl-1,3-sultone, ethylene sulfate, propylene sulfate, butylene sulfite, vinylene carbonate and fluoroethylene carbonate, more preferably 1,3-propane sultone, 1,4-butane sultone, propenyl-1,3-sultone, ethylene sulfate, propylene sulfate, butylene sulfite, vinylene carbonate or fluoroethylene carbonate.
In the present invention, the mass content of the first auxiliary additive in the electrolyte is preferably 0.1% to 3.0%, more preferably 0.5% to 2.5%, and more preferably 1.0% to 2.0%.
In the present invention, the electrolyte preferably includes a second auxiliary additive.
In the present invention, the second auxiliary additive preferably includes one or more of lithium bis-fluorosulfonylimide, lithium difluorooxalato borate, lithium difluorooxalato phosphate, lithium difluorophosphate, and lithium tetrafluoroborate, and more preferably lithium bis-fluorosulfonylimide, lithium difluorooxalato borate, lithium difluorooxalato phosphate, lithium difluorophosphate, or lithium tetrafluoroborate.
In the present invention, the molar content of the second auxiliary additive in the electrolyte solution is preferably 0.001 to 1.0M, more preferably 0.01 to 0.5M, and still more preferably 0.1 to 0.2M.
The invention is a complete and detailed integral technical scheme, better ensures the lithium supplementing effect of the anode lithium supplementing agent, further reduces the gas production rate, improves the stability and the cycle life of the lithium ion battery, and has the lithium ion conductivity, and the lithium ion battery preferably comprises: positive pole, negative pole, electrolyte, diaphragm. The negative electrode comprises a negative electrode active material, a negative electrode conductive agent and a negative electrode binder, and the positive electrode comprises a positive electrode active material, a positive electrode conductive agent, a positive electrode binder and a lithium supplement additive.
The positive active material may include, but is not limited to, at least one of lithium cobaltate, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, lithium vanadate, lithium manganate, lithium nickelate, lithium nickel cobalt manganate, lithium rich manganese based material, lithium nickel cobalt aluminate, and lithium titanate.
Further, the positive electrode conductive agent is selected from one or more of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene or carbon nanotubes.
Further, the positive electrode binder is selected from one or more of polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene or polyhexafluoropropylene.
Further, the application of the lithium ion battery anode lithium supplement additive in lithium ion battery anode lithium supplement is that in the anode pulping process, the lithium ion battery anode lithium supplement additive is uniformly mixed with an anode active material, a conductive agent, a binder and a solvent, and then the anode pole piece is prepared through coating, rolling and drying.
Further, the lithium ion battery anode lithium supplement additive, the anode active material, the conductive agent and the binder are counted as a whole, and the mass percentage of each component is as follows: 75 to 97.5 percent of positive active material, 1 to 10 percent of conductive agent, 1 to 10 percent of binder and 0.5 to 5 percent of lithium supplement additive for the positive electrode of the lithium ion battery
Further, the negative active material is selected from one or more of graphite and silicon-based materials.
Further, the negative electrode conductive agent is selected from one or more of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene or carbon nanotubes; the negative electrode binder is selected from one or more of polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene or polyhexafluoropropylene.
Further, the electrolyte also comprises: at least one of ethylene carbonate, propylene carbonate, methylethyl carbonate, dimethyl carbonate, diethyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, dimethyl ether, diethyl ether, adiponitrile, succinonitrile, glutaronitrile, dimethyl sulfoxide, sulfolane, 1,4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate, butyl propionate and ethyl butyrate, wherein the mass percentage of the at least one of the ethylene carbonate, the propylene carbonate, the methylethyl carbonate, the dimethyl carbonate, the diethyl carbonate, the methylpropyl carbonate, the ethylpropyl formate, the dimethyl sulfoxide, the sulfolane, the 1,4-butyrolactone, the methyl formate, the ethyl acetate, the methyl propionate, the ethyl propionate, the butyl propionate and the ethyl butyrate are 50-98%;
further, the electrolyte also comprises: one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate and lithium bis-fluorosulfonyl imide, and the mass percentage of the lithium hexafluorophosphate, the lithium tetrafluoroborate, the lithium perchlorate and the lithium bis-fluorosulfonyl imide in the electrolyte is 1 to 18 percent.
Furthermore, the auxiliary additive 1,3-propane sultone, 1,4-butane sultone, propenyl-1,3-sultone, ethylene sulfate, propylene sulfate, butylene sulfite, vinylene carbonate or fluoroethylene carbonate accounts for 0.1-3.0% of the total mass of the electrolyte; the auxiliary additive is lithium bis (fluorosulfonyl) imide, lithium difluoro (oxalato) borate, lithium difluoro (oxalato) phosphate or lithium tetrafluoroborate, and the molar content of the auxiliary additive in the electrolyte is 0-1.0M.
The invention provides an organic lithium salt lithium supplement material and a lithium ion battery. The invention designs a cyano phosphate additive with a specific structure and composition, which is an organic lithium salt lithium supplement material for lithium supplement of a lithium ion battery anode. The positive electrode lithium supplement material contains cyano functional groups, and can be complexed with metal ions to inhibit the diffusion of the metal ions to electrolyte, so that the catalytic reaction of the metal ions to an organic solvent is reduced, the gas production is reduced, and the high-temperature cycle performance is improved. Meanwhile, the presence of the positive electrode additive can improve the appearance and the components of the CEI film, and promote and participate in the component Li x PO y F z The formation of (2) reduces the film resistance, reduces the polarization, reduces the consumption of lithium ions, and improves the efficiency. And the positive electrode lithium supplement additive is insensitive to moisture, has excellent stability in air, can reduce the requirement on the environment in the preparation process of the positive electrode plate, and is a positive electrode lithium supplement agent with great potential.
The organic lithium phosphate compound containing the cyano group provided by the invention is used as a lithium supplement material, and can be complexed with metal ions from the aspect of performance so as to inhibit the diffusion of the metal ions to an electrolyte, further reduce the catalytic reaction of the metal ions to an organic solvent, reduce the gas production and improve the high-temperature cycle performance; and the lithium supplement agent contains phosphate groups, the existence of the structure improves the appearance and the components of the CEI film, and promotes and participates in the component Li x PO y F z The formation of the phosphate ester group reduces the film impedance, reduces the polarization, reduces the consumption of lithium ions, improves the efficiency, ensures that the phosphate ester group is less prone to generate gas compared with a carbonate lithium supplement agent, has flame retardant property and improves the safety of the battery; meanwhile, the lithium supplement agent can also introduce corresponding groups according to the needs to match the needs of practical application; in addition, the lithium supplement agent is not sensitive to moisture and oxygen, so that a battery prepared by using the lithium supplement agent does not need special environment.
The positive organic lithium salt lithium supplement agent provided by the invention has the advantages of low gas production rate, good stability and long cycle life, can well improve the conductivity of lithium ions, is a positive lithium supplement additive with excellent comprehensive performance, and can be used for reducing the gas production rate and improving the stability, energy density and high-temperature storage performance of lithium ion batteries.
Experimental results show that the existence of cyano functional groups in the positive organic lithium salt lithium supplement agent provided by the invention can prolong the cycle life of the battery and reduce the gas yield; the lithium supplement additive contains F, so that the internal resistance of the battery can be reduced, and the cycle life, high-temperature storage and other performances of the battery can be improved by using the additive.
For further illustration of the present invention, a cyanophosphate additive and a lithium ion battery provided by the present invention will be described in detail with reference to the following examples, but it should be understood that the examples are carried out on the premise of the technical scheme of the present invention, and the detailed embodiments and the specific operation procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of the present invention is not limited to the following examples.
The reagents used in the following examples of the present invention are all commercially available.
Example 1
Preparing a positive plate: liNi as positive electrode active material 0.6 Co 0.2 Mn 0.2 O 2 The positive electrode lithium supplement material structure (1), the positive electrode conductive agent acetylene black and the positive electrode binder polyvinylidene fluoride are mixed according to the mass ratio of 92;
preparing a negative plate: mixing SiO @ C (amorphous carbon-coated silica, wherein the amorphous carbon coating amount is 3% of the mass of SiO), graphite, a negative electrode conductive agent carbon black, a negative electrode adhesive carboxymethylcellulose sodium and styrene butadiene rubber in a mass ratio of 1.5;
and assembling the prepared positive plate and the prepared negative plate into the 2Ah soft-package battery cell.
Example 2
Preparing a positive plate: liNi as positive electrode active material 0.6 Co 0.2 Mn 0.2 O 2 The positive electrode lithium supplement material structure (2), the positive electrode conductive agent carbon nano tube and the positive electrode binder polyvinylidene fluoride are mixed according to the mass ratio of 92;
preparing a negative plate: mixing SiO @ C (amorphous carbon-coated silica, wherein the coating amount of amorphous carbon is 3% of the mass of SiO), graphite, a negative electrode conductive agent carbon black and a negative electrode binder polyacrylic acid according to the mass ratio of 11.5;
and assembling the prepared positive plate and the prepared negative plate into the 2Ah soft-package battery cell.
Example 3
Preparing a positive plate: liN as a positive electrode active material i0.6 Co 0.2 Mn 0.2 O 2 The positive electrode lithium supplement material structure (3), the positive electrode conductive agent carbon nano tube and the positive electrode binder polyvinylidene fluoride are mixed according to the mass ratio of 92;
preparing a negative plate: mixing SiO @ C (amorphous carbon-coated silicon oxide, wherein the coating amount of amorphous carbon is 5% of the mass of SiO), graphite, a negative electrode conductive agent acetylene black and a negative electrode binder polyvinylidene fluoride according to the mass ratio of 11.5;
and assembling the prepared positive plate and the prepared negative plate into the 2Ah soft-package battery cell.
Example 4
Preparing a positive plate: liCoO as positive electrode active material 2 The positive electrode lithium supplement material structure (4), the positive electrode conductive agent acetylene black and the positive electrode binder polyvinylidene fluoride are mixed according to the mass ratio of 92;
preparing a negative plate: mixing graphite, a negative electrode conductive agent carbon black, a negative electrode binder carboxymethylcellulose sodium and styrene butadiene rubber according to the mass ratio of 95.5;
and assembling the prepared positive plate and the prepared negative plate into the 2Ah soft-package battery cell.
Example 5
Preparing a positive plate: liCoO as positive electrode active material 2 The positive electrode lithium supplement material structure (5), the positive electrode conductive agent acetylene black and the positive electrode binder polyvinylidene fluoride are mixed according to the mass ratio of 92;
preparing a negative plate: mixing graphite, a negative electrode conductive agent carbon black, a negative electrode binder carboxymethylcellulose sodium and styrene butadiene rubber according to the mass ratio of 95.5;
and assembling the prepared positive plate and the prepared negative plate into a 2Ah soft package battery cell.
Example 6
Preparing a positive plate: liCoO as positive electrode active material 2 The positive electrode lithium supplement material structure (6), the positive electrode conductive agent acetylene black and the positive electrode binder polyvinylidene fluoride are mixed according to the mass ratio of 92;
preparing a negative plate: mixing graphite, a negative electrode conductive agent carbon black, a negative electrode binder carboxymethylcellulose sodium and styrene butadiene rubber according to the mass ratio of 95.5;
and assembling the prepared positive plate and the prepared negative plate into the 2Ah soft-package battery cell.
Example 7
Preparing a positive plate: liNi as positive electrode active material 0.6 Co 0.2 Mn 0.2 O 2 The positive electrode lithium supplement material structure (7), the positive electrode conductive agent carbon nanotube and the positive electrode binder polyvinylidene fluoride are mixed according to the mass ratio of 94;
preparing a negative plate: mixing SiO @ C (amorphous carbon-coated silica, wherein the coating amount of amorphous carbon is 3% of the mass of SiO), graphite, a negative electrode conductive agent carbon black and a negative electrode binder polyacrylic acid according to the mass ratio of 11.5;
and assembling the prepared positive plate and the prepared negative plate into the 2Ah soft-package battery cell.
Example 8
Preparing a positive plate: liNi as positive electrode active material 0.6 Co 0.2 Mn 0.2 O 2 The positive electrode lithium supplement material structure (8), the positive electrode conductive agent carbon nano tube and the positive electrode binder polyvinylidene fluoride are mixed according to the mass ratio of 92;
preparing a negative plate: mixing SiO @ C (amorphous carbon-coated silica, wherein the coating amount of amorphous carbon is 3% of the mass of SiO), graphite, a negative electrode conductive agent carbon black and a negative electrode binder polyacrylic acid according to the mass ratio of 11.5;
and assembling the prepared positive plate and the prepared negative plate into the 2Ah soft-package battery cell.
Example 9
Preparing a positive plate: liNi as positive electrode active material 0.6 Co 0.2 Mn 0.2 O 2 The positive electrode lithium supplement material structure (8), the positive electrode conductive agent carbon nano tube and the positive electrode binder polyvinylidene fluoride are mixed according to the mass ratio of 94;
preparing a negative plate: mixing SiO @ C (amorphous carbon-coated silica, wherein the coating amount of amorphous carbon is 3% of the mass of SiO), graphite, a negative electrode conductive agent carbon black and a negative electrode binder polyacrylic acid according to the mass ratio of 11.5;
and assembling the prepared positive plate and the prepared negative plate into the 2Ah soft-package battery cell.
Example 10
Preparing a positive plate: liNi as positive electrode active material 0.6 Co 0.2 Mn 0.2 O 2 The positive electrode lithium supplement material structure (9), the positive electrode conductive agent carbon nanotube and the positive electrode binder polyvinylidene fluoride are mixed according to the mass ratio of 94;
preparing a negative plate: mixing SiO @ C (amorphous carbon-coated silica, wherein the coating amount of amorphous carbon is 3% of the mass of SiO), graphite, a negative electrode conductive agent carbon black and a negative electrode binder polyacrylic acid according to the mass ratio of 11.5;
and assembling the prepared positive plate and the prepared negative plate into a 2Ah soft package battery cell.
Example 11
Preparing a positive plate: liNi as positive electrode active material 0.6 Co 0.2 Mn 0.2 O 2 Mixing the positive electrode lithium supplement material structure, positive electrode conductive agent carbon nano tubes and positive electrode binder polyvinylidene fluoride according to a mass ratio of 92;
preparing a negative plate: mixing SiO @ C (amorphous carbon-coated silicon oxide, wherein the coating amount of amorphous carbon is 5% of the mass of SiO), graphite, a negative electrode conductive agent acetylene black and a negative electrode binder polyvinylidene fluoride according to the mass ratio of 11.5;
and assembling the prepared positive plate and the prepared negative plate into the 2Ah soft-package battery cell.
Example 12
Preparing a positive plate: liCoO as positive electrode active material 2 The structure of the lithium-supplementing material for the positive electrode
Mixing a positive electrode conductive agent acetylene black and a positive electrode binder polyvinylidene fluoride according to a mass ratio of 92;
preparing a negative plate: mixing graphite, a negative electrode conductive agent carbon black, a negative electrode binder carboxymethylcellulose sodium and styrene butadiene rubber according to the mass ratio of 95.5;
and assembling the prepared positive plate and the prepared negative plate into the 2Ah soft-package battery cell.
Comparative example 1
The operation is the same as that of the embodiment 1 except that no lithium supplement agent is added at the positive terminal;
comparative example 2
The operation is the same as that of example 4 except that no lithium supplement agent is added at the positive terminal;
comparative example 3
Lithium salt without cyano group is added at the positive end, and the structure is shown in the figure
The others are in accordance with example 1;
the lithium supplement agent is not sensitive to moisture and oxygen, so the experiment does not need to particularly control the environment for preparing the pole piece.
The preparation method of the battery comprises the following steps:
and determining the coating surface density according to the capacity design (2000 mAh) of the battery and the capacities of the anode and cathode materials.
The electrolyte comprises the following components: 1.1MLiPF 6 ，EC：EMC＝30：70，1％VC，1％FEC。
Preparing a lithium ion battery: and (3) making a square battery cell by winding the positive plate, the negative plate and the diaphragm (PE film containing the ceramic coating) of the lithium ion battery prepared by the process, placing the bare battery cell in an outer package, injecting the prepared electrolyte into the dried battery, and performing the procedures of packaging, standing, formation, shaping, capacity grading and the like to finish the preparation of the lithium ion battery.
In order to verify the performance of the product, the 2Ah soft-packaged cells prepared in examples 1 to 12 and comparative examples 1 to 3 were subjected to performance testing, the specific method is as follows, and the results are shown in table 1.
(1) First-effect test of the battery core: first circle discharge capacity of battery core/first circle charge capacity of battery core.
(2) And (3) testing the gram capacity of the first circle of the positive electrode of the battery core: the first circle discharge capacity mAh of the battery core/the mass g of the positive active material.
(3) Testing the direct current internal resistance DCR of the battery core: capacity grading and adjusting the battery to 50% soc,5c 10S discharge, testing the discharge resistance, resistance DCR = (V0-V10)/I, where V0 is the potential before discharge, V10 is the 10 th S potential after discharge, and I is the discharge current 2C;
(4) Capacity retention at 45 ℃ test: (1) charging: charging to 4.2V at constant current and constant voltage at 1C, and standing for 10min; (2) discharging: discharging the 1C to 2.8V at constant current; (3) repeat (1), (2) "500 cycles.
After 500 cycles of charge and discharge, the capacity retention rate of the 500 th cycle is calculated, and the calculation formula is as follows:
capacity retention (%) at 500 cycles = (500 cycles discharge capacity/1 cycles discharge capacity) × 100%.
The upper limit of the voltage cycle interval of the lithium cobaltate system, namely the voltage cycle interval of the example 456 and the comparative example 2, is changed to 4.45V, and the rest is unchanged.
(5) High temperature storage testing
Dividing the capacity of 1C at the room temperature of 25 ℃ under the battery cell to obtain the capacity which is marked as D0;
fully charging the battery cell 1C, then placing the battery cell in a 60 ℃ oven for high-temperature storage for 20D, then taking out the battery cell, testing the recovery capacity after cooling at room temperature, recording the recovery capacity as D1, and calculating the recovery rate of the high-temperature storage capacity of the battery cell: D1/D0
(6) High temperature gassing test
Fully charging the battery cell, testing the initial volume V0 by adopting an elimination method, then placing the battery cell in a 60 ℃ oven, standing for 30D, and testing the volume V1 by using a drainage method, wherein the growth rate of the high-temperature gas production volume is V1/V0-1.
Referring to table 1, table 1 shows the performance test data of the soft package cells prepared in examples 1 to 12 and comparative examples 1 to 3 according to the present invention.
TABLE 1
As can be seen from table 1, the first effect, first loop positive electrode gram capacity, internal resistance, capacity retention, high temperature storage and gas generation of the 2Ah soft package cells prepared in examples 1 to 12 are significantly improved compared with those of comparative examples 1 to 2 in examples 1 to 12.
Comparison of example 1 with example 2 shows that the presence of multiple cyano functions increases the cycle life of the cell and decreases the gas generation rate;
compared with the comparative example 3, the embodiment 1 shows that the lithium supplement agent containing the cyano is more beneficial to inhibiting gas generation and prolonging the cycle life of the battery;
comparing the example 4 with the example 5, the lithium supplement additive contains F, which is beneficial to reducing the internal resistance of the battery;
comparing example 5 with example 8, it can be seen that, in the positive electrode lithium supplement additive, the higher the lithium content, the more lithium can be provided in the process of lithium supplement of the corresponding positive electrode, the better the lithium supplement effect is, and the higher the first effect/the better the gram capacity of the positive electrode is.
Referring to fig. 3, fig. 3 is a graph comparing the capacity retention rates of example 1 of the present invention and comparative example 1.
Referring to fig. 4, fig. 4 is a box plot of the first efficiencies of example 1, comparative example 1, example 4 and comparative example 2 of the present invention.
In conclusion, the organic anode lithium supplement material provided by the invention has a good lithium supplement effect, can effectively inhibit gas generation, reduce internal resistance and prolong the high-temperature cycle life.
The foregoing detailed description of an organic lithium salt lithium supplement material and lithium ion battery provided by the present invention, and the principles and embodiments of the present invention are described herein using specific examples, which are provided only to facilitate the understanding of the method and its core ideas, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any combination of the methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A cyanophosphate additive, wherein said additive has the structure of formula (I):
wherein, R is 1 Selected from cyano-containing groups;
the R is 2 Selected from lithium ions, saturated hydrocarbon groups of C1-C6, unsaturated hydrocarbon groups of C1-C6, alkoxy groups, cyanoalkyl groups, halogenated alkyl groups, phenyl groups, silane groups or substituted silane groups.
2. The additive of claim 1 wherein the cyano-containing group comprises a cyanoalkyl group or a substituted cyanoalkyl group;
the substitution includes halogen substitution;
the cyano phosphate additive is a positive electrode additive;
the positive electrode comprises a lithium ion battery positive electrode.
3. The additive of claim 1, wherein the additive has a structure represented by any one of formulas (1) to (11):
4. the additive as claimed in claim 1, wherein the additive is a positive electrode organic lithium salt lithium-supplementing material;
the mass ratio of the cyanophosphate additive to the positive active material is (0.5-5): (75-97.5);
the cyano phosphate additive is a positive electrode additive for improving the appearance and/or components of the CEI film;
the cyanophosphate additive promotes and participates in the component Li x PO y F z Is performed.
5. A lithium ion battery is characterized by comprising a positive electrode, a negative electrode and electrolyte;
the positive electrode includes the cyanophosphate additive according to any one of claims 1 to 4.
6. The lithium ion battery of claim 5, wherein the positive electrode further comprises a positive active material, a positive conductive agent, and a positive binder;
the positive active material comprises one or more of lithium cobaltate, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, lithium vanadate, lithium manganate, lithium nickelate, lithium nickel cobalt manganese oxide, a lithium-rich manganese-based material, lithium nickel cobalt aluminate and lithium titanate;
the positive electrode conductive agent comprises one or more of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene and carbon nanotubes;
the positive binder comprises one or more of polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene and polyhexafluoropropylene;
the preparation process of the positive electrode comprises the steps of uniformly mixing the cyanophosphate additive, the positive electrode active material, the positive electrode conductive agent, the positive electrode binder and the solvent in the positive electrode pulping process, and then coating, rolling and drying to obtain the positive electrode sheet.
7. The lithium ion battery of claim 6, wherein the positive electrode comprises 75-97.5% by mass of the positive electrode active material based on the total amount of the cyanophosphate additive, the positive electrode active material, the positive electrode conductive agent and the positive electrode binder;
the anode is integrally calculated by using a cyano phosphate additive, an anode active material, an anode conductive agent and an anode binder, and the mass content of the anode conductive agent is 1-10%;
the anode is integrally calculated by using a cyanophosphate additive, an anode active material, an anode conductive agent and an anode binder, and the mass content of the anode binder is 1-10%;
the anode is integrally calculated by using a cyanophosphate additive, an anode active material, an anode conductive agent and an anode binder, and the mass content of the cyanophosphate additive is 0.5-5%.
8. The lithium ion battery of claim 5, wherein the negative electrode comprises a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder;
the negative active material comprises graphite and/or a silicon-based material;
the negative electrode conductive agent comprises one or more of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene and carbon nano tubes;
the negative electrode binder comprises one or more of polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene and polyhexafluoropropylene.
9. The lithium ion battery of claim 5, wherein the electrolyte comprises a solvent;
the solvent comprises one or more of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, dimethyl ether, diethyl ether, adiponitrile, succinonitrile, glutaronitrile, dimethyl sulfoxide, sulfolane, 1,4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate, butyl propionate and ethyl butyrate;
the mass content of the solvent in the electrolyte is 50-98%;
the electrolyte includes a lithium salt;
the lithium salt comprises one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate and lithium bis (fluorosulfonyl) imide;
the mass content of the lithium salt in the electrolyte is 1-18%.
10. The lithium ion battery of claim 5, wherein the electrolyte comprises a first auxiliary additive;
the first auxiliary additive comprises one or more of 1,3-propane sultone, 1,4-butane sultone, propenyl-1,3-sultone, ethylene sulfate, propylene sulfate, butylene sulfite, vinylene carbonate and fluoroethylene carbonate;
the mass content of the first auxiliary additive in the electrolyte is 0.1-3.0%;
the electrolyte comprises a second auxiliary additive;
the second auxiliary additive comprises one or more of lithium bis-fluorosulfonylimide, lithium difluorooxalato borate, lithium difluorooxalato phosphate, lithium difluorophosphate and lithium tetrafluoroborate;
the molar content of the second auxiliary additive in the electrolyte is 0.001-1.0M.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116936810A (en) * | 2023-09-15 | 2023-10-24 | 天鹏锂能技术(淮安)有限公司 | Positive pole piece of sodium ion battery and sodium ion battery |
| CN116960466A (en) * | 2023-09-15 | 2023-10-27 | 宁德时代新能源科技股份有限公司 | Electrolyte, secondary battery and electricity utilization device |
| CN117334917A (en) * | 2023-12-01 | 2024-01-02 | 宁德时代新能源科技股份有限公司 | Secondary battery and electricity utilization device |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116936810A (en) * | 2023-09-15 | 2023-10-24 | 天鹏锂能技术(淮安)有限公司 | Positive pole piece of sodium ion battery and sodium ion battery |
| CN116960466A (en) * | 2023-09-15 | 2023-10-27 | 宁德时代新能源科技股份有限公司 | Electrolyte, secondary battery and electricity utilization device |
| CN116936810B (en) * | 2023-09-15 | 2023-12-12 | 天鹏锂能技术(淮安)有限公司 | Positive pole piece of sodium ion battery and sodium ion battery |
| CN116960466B (en) * | 2023-09-15 | 2024-04-02 | 宁德时代新能源科技股份有限公司 | Electrolyte, secondary battery and electricity utilization device |
| CN117334917A (en) * | 2023-12-01 | 2024-01-02 | 宁德时代新能源科技股份有限公司 | Secondary battery and electricity utilization device |
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