CN115611773B - Lithium supplementing compound, preparation method thereof and lithium ion battery - Google Patents
Lithium supplementing compound, preparation method thereof and lithium ion battery Download PDFInfo
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- CN115611773B CN115611773B CN202211347382.6A CN202211347382A CN115611773B CN 115611773 B CN115611773 B CN 115611773B CN 202211347382 A CN202211347382 A CN 202211347382A CN 115611773 B CN115611773 B CN 115611773B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 218
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 213
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 143
- 150000001875 compounds Chemical class 0.000 title claims abstract description 97
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000001308 synthesis method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims description 28
- 239000006258 conductive agent Substances 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 17
- -1 polypropylene Polymers 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000005287 vanadyl group Chemical group 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 2
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 15
- 239000000047 product Substances 0.000 abstract description 12
- 239000013589 supplement Substances 0.000 abstract description 12
- 239000002000 Electrolyte additive Substances 0.000 abstract description 8
- 239000010405 anode material Substances 0.000 abstract description 3
- 230000000536 complexating effect Effects 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 231100000989 no adverse effect Toxicity 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000006138 lithiation reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000009469 supplementation Effects 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/11—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton
- C07C255/12—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton containing cyano groups and hydroxy groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a chain lithium supplementing compound, which has a structure shown in a formula (I). In the structure of the chain lithium-supplementing compound, the-OLi group is used for supplementing lithium for the lithium ion battery, the-CN group is used after the chain lithium-supplementing compound supplements lithium and enters the electrolyte, and the-CN group has a strong complexing effect with transition metal in the anode material, so that a layer of film is formed on the surface of the anode of the lithium ion battery, the dissolution of transition metal ions is inhibited, and the anode is protected. The synthesis method of the chain lithium supplementing compound provided by the invention is simple, and the lithium supplementing process is clear, and the chain lithium supplementing compound contains 3-OLi groups, so that the lithium supplementing effect is better. The lithium supplementing reaction after the power is supplied, the product after the lithium supplementing reaction has no adverse effect on the battery, and the lithium supplementing reaction can be used as an electrolyte additive.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery positive electrode materials, and relates to a chain lithium supplementing compound, a synthesis method thereof and a lithium ion battery, in particular to a lithium supplementing compound, a preparation method thereof and a lithium ion battery.
Background
With the continuous development of new energy industry, lithium ion batteries are widely concerned, and the improvement of energy density is the key point of future development. In the current situation, the easier realization method for improving the energy density of the lithium ion battery is that the ternary materials (NCM, NCA) are rapidly developed in recent years in order to adapt to the requirement of gradually increasing energy density of the battery in the aspect of the positive electrode material of the battery, and are successfully widely applied in a lithium ion battery system; in the aspect of the cathode, the graphite material is used as a cathode material of a lithium ion battery which is widely used, has the advantages of wide sources, rich reserves, stable electrochemical performance and the like, but has the defects of obvious defects, namely insufficient gram capacity, active lithium loss in the first charge and discharge process, and the defect can compensate the irreversible capacity loss of the lithium ion battery by a method of supplementing lithium in advance, so that the capacity of the battery is recovered, thereby improving the energy density of the lithium ion battery, and has been widely studied in recent years.
The pre-lithiation technology has been developed rapidly in recent years, and is helpful to the improvement of the energy density and the first coulombic efficiency of lithium ion batteries. It is known that during the first charge and discharge cycle of a lithium ion battery, a protective film, i.e., a solid electrolyte interface film (SEI film), is formed on the surface of the negative electrode by oxidation-reduction reaction, lithium from the positive electrode is consumed during this process, and this consumption of lithium is irreversibly and permanently consumed, which results in the first cycle efficiency and energy density of the lithium ion battery. The pre-lithiation technology is to supplement lithium to the negative electrode or indirectly supplement lithium to the negative electrode through the positive electrode before the first charge and discharge of the lithium ion battery so as to compensate the lithium loss on the negative electrode caused by the formation of the SEI film. The lithium ion battery lithium supplementing technology has been widely studied, and the lithium supplementing modes disclosed at present are numerous and mainly comprise two major categories of positive electrode lithium supplementing and negative electrode lithium supplementing. Earlier research on negative electrode lithium supplement mainly comprises a plurality of lithium supplement modes such as physical method lithium supplement, self-discharge lithium supplement, chemical lithium supplement, electrochemical lithium supplement and the like based on metal lithium, and the lithium supplement technology based on metal lithium is mature, wherein lithium powder and lithium foil are widely used, however, because the physical and chemical properties of the metal lithium are very sensitive, the accuracy of pre-lithiation is still very difficult to control, and corresponding pre-lithiation operation is required to be carried out under extremely strict inert atmosphere, which is difficult to realize for large-scale application. Therefore, it is necessary to explore new prelithiation techniques to solve various problems caused by lithium metal.
In recent years, the positive electrode pre-lithiation technology is widely paid attention to, and a new solution idea is provided for realizing commercial application of the lithium supplementing technology. Compared with the cathode lithium supplementing technology, the cathode lithium supplementing technology has the advantages of good safety and simple operation, but the defect that the cathode lithium supplementing additive can lead to the reduction of the proportion of the cathode active material, and gas production or solid residues after lithium supplementing cause bad influence on the performance of the battery.
Therefore, how to obtain a more suitable lithium supplementing material, especially for the lithium supplementing agent of the positive electrode, has better lithium supplementing effect, solves the problems existing in the prior lithium supplementing agent, and becomes one of the problems to be solved by a plurality of first-line researchers in the industry.
Disclosure of Invention
In view of the above, the invention provides a chain lithium supplementing compound, a synthesis method thereof and a lithium ion battery. The chain lithium supplementing compound provided by the invention not only can realize effective lithium supplementation of a lithium ion battery, but also has the advantages of low cost, high safety and simple synthesis, the subsequent circulation of the battery is not affected after lithium supplementation, and a product after lithium supplementation is soluble in electrolyte and serves as an electrolyte additive.
The invention provides a chain lithium supplementing compound, which has a structure shown in a formula (I):
Wherein n is the degree of polymerization.
Preferably, n is more than or equal to 0 and less than or equal to 5;
the chain lithium-supplementing compound has one of structures represented by formulas (1) to (4):
preferably, the chain lithium supplementing compound is an anode lithium supplementing material;
The positive electrode comprises a positive electrode of a lithium ion battery;
the mass ratio of the chain lithium supplementing compound to the positive electrode active material in the positive electrode of the lithium ion battery is (1-10): (70-80).
The invention provides a synthesis method of a chain lithium supplementing compound according to any one of the technical schemes, which comprises the following steps:
1) Dissolving chain raw materials with a structure of a specific formula (II) and a lithium source in a solvent to react to obtain a chain lithium supplementing compound;
Wherein n is the degree of polymerization.
Preferably, n is more than or equal to 0 and less than or equal to 5;
the mol ratio of the chain raw material to the lithium source is 1 (3.1-3.4);
The lithium source includes one or more of lithium hydride, lithium nitride, and n-butyllithium.
Preferably, the solvent comprises one or more of an ether solvent, benzene and toluene;
the reaction time is 5-24 hours;
The reaction may further comprise a filtration and/or drying step.
Preferably, the drying mode comprises vacuum drying;
the drying time is 2-12 hours;
the drying temperature is 60-150 ℃.
The invention also provides a lithium ion battery, which comprises an anode, a cathode and nonaqueous lithium ion battery electrolyte;
The positive electrode contains the chain lithium supplementing compound according to any one of the above technical schemes or the chain lithium supplementing compound synthesized by the synthesis method according to any one of the above technical schemes.
Preferably, the positive electrode includes a positive electrode active material, a chain lithium supplementing compound, a conductive agent, and a binder;
the positive electrode 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 manganate, lithium-rich manganese-based material, lithium nickel cobalt aluminate and lithium titanate;
The conductive agent comprises one or more of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene and carbon nano tubes;
the binder comprises one or more of polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene and polyhexafluoropropylene.
Preferably, the positive electrode is formed by taking a chain lithium supplementing compound, a positive electrode active material, a conductive agent and a binder as a whole, wherein the mass content of the positive electrode active material is 70-80%;
the positive electrode is formed by taking a chain lithium supplementing compound, a positive electrode active material, a conductive agent and a binder as a whole, wherein the mass content of the conductive agent is 1% -10%;
the positive electrode is formed by taking a chain lithium supplementing compound, a positive electrode active material, a conductive agent and a binder as a whole, wherein the mass content of the binder is 1-10%;
the positive electrode is formed by taking a chain lithium supplementing compound, a positive electrode active material, a conductive agent and a binder as a whole, wherein the mass content of the chain lithium supplementing compound is 1-10%.
The invention provides a chain lithium supplementing compound, which has a structure shown in a formula (I). Compared with the prior art, the invention particularly designs a chain lithium supplementing compound with a specific structure for the pre-lithiation of the lithium ion battery in the field of the pre-lithiation of the lithium ion battery. In the structure of the chain lithium-supplementing compound, the-OLi group is used for supplementing lithium for the lithium ion battery, the-CN group is used after the chain lithium-supplementing compound supplements lithium and enters the electrolyte, and the-CN group has a strong complexing effect with transition metal in the anode material, so that a layer of film is formed on the surface of the anode of the lithium ion battery, the dissolution of transition metal ions is inhibited, and the anode is protected.
The chain lithium supplementing compound disclosed by the invention belongs to positive electrode lithium supplementing, the use method is simple, the chain lithium supplementing compound is added together with an active substance of a positive electrode material in the process of preparing slurry of a positive electrode plate, the chain lithium supplementing compound can improve the first charge-discharge specific capacity of a lithium ion battery, a product after lithium supplementing is soluble in electrolyte, and the product after lithium supplementing can be used as an electrolyte additive, so that a protective film can be formed at the positive electrode, and the cycle performance of the battery is improved. The synthesis method of the chain lithium supplementing compound provided by the invention is simple, and the lithium supplementing process is clear, and the chain lithium supplementing compound contains 3-OLi groups, so that the lithium supplementing effect is better. The lithium supplementing reaction after the power is supplied, the product after the lithium supplementing reaction has no adverse effect on the battery, and the lithium supplementing reaction can be used as an electrolyte additive.
Compared with the prior art that lithium powder or lithium foil is mainly used for supplementing lithium to the negative electrode, the method is subject to the problems that the instability of lithium, the difficulty of the process technology and the use condition are severe, the negative electrode lithium supplementing technology still cannot be applied on a large scale, and the like. Compared with the existing positive electrode lithium supplementing method, the lithium supplementing additive mainly has the defects that gas production (such as O 2, N 2 and the like) and residual metal oxide without activity can cause capacity attenuation and safety problems on the battery, and the battery needs to be sealed after the gas is completely released in the use process, so that the battery is not beneficial to various limitations such as industrial production and the like. The chain compound provided by the invention can not generate gas and have no solid substance residue in the lithium supplementing process, and the product after lithium supplementing can be dissolved in battery electrolyte, and meanwhile, the product structure contains nitrile groups, so that the chain compound can be used as an electrolyte additive for stabilizing the anode, and is beneficial to the electrochemical performance of the battery. The invention also discloses a lithium supplementing positive electrode containing the chain lithium supplementing compound and a lithium ion battery assembled by adopting the lithium supplementing positive electrode.
The experimental result shows that the first charge and discharge efficiency of the lithium ion battery assembled without adding the lithium supplementing agent is 87.48%. Active lithium loss results from the permanent consumption of Li + in the film formation of the graphite anode. The lithium ion battery after adding the positive electrode lithium supplementing agent provided by the invention has different degree of reduction in the first charge and discharge efficiency, which is caused by incapability of back intercalation after Li + in the chain-shaped lithium supplementing compound is delithiated. After the lithium supplementing agent is added, the first-time charging specific capacity and the first-time discharging specific capacity of the battery are improved to different degrees, and the lithium supplementing effect is good.
Detailed Description
For further understanding of the present invention, the technical aspects of the present invention will be clearly and fully described in connection with the following embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
All raw materials of the invention are not particularly limited in purity, and the invention preferably adopts analytically pure or conventional purity in the field of preparation of lithium ion battery anode lithium supplementing materials.
The invention provides a chain lithium supplementing compound, which has a structure shown in a formula (I):
Wherein n is the degree of polymerization.
In the present invention, the chain lithium supplementing compound is preferably 0.ltoreq.n.ltoreq.5, more preferably 1.ltoreq.n.ltoreq.4, and still more preferably 2.ltoreq.n.ltoreq.3.
In the present invention, the chain lithium-supplementing compound preferably has one of the structures represented by formulas (1) to (4):
In the present invention, the chain lithium supplementing compound is preferably a positive electrode lithium supplementing material.
In the present invention, the chain lithium supplementing compound is preferably a positive electrode lithium supplementing material for pre-lithiation of a lithium ion battery.
In the present invention, the positive electrode preferably includes a lithium ion battery positive electrode, more preferably a pre-lithiated positive electrode.
In the present invention, the mass ratio of the chain lithium-supplementing compound to the positive electrode active material in the positive electrode of the lithium ion battery is preferably (1 to 10): (70 to 80), more preferably (4 to 7): (70 to 80), more preferably (1 to 10): (74-76).
The invention provides a synthesis method of the chain lithium supplementing compound according to any one of the technical schemes, which comprises the following steps:
1) Dissolving chain raw materials with a structure of a specific formula (II) and a lithium source in a solvent to react to obtain a chain lithium supplementing compound;
Wherein n is the degree of polymerization.
In the present invention, the synthesis method is preferably 0.ltoreq.n.ltoreq.5, more preferably 1.ltoreq.n.ltoreq.4, and still more preferably 2.ltoreq.n.ltoreq.3.
In the present invention, the molar ratio of the chain raw material to the lithium source is preferably 1 (3.1 to 3.4), more preferably 1 (3.15 to 3.35), and still more preferably 1 (3.2 to 3.3).
In the present invention, the lithium source preferably includes one or more of lithium hydride, lithium nitride and n-butyllithium, more preferably lithium hydride, lithium nitride or n-butyllithium.
In the present invention, the solvent preferably includes one or more of an ether solvent, benzene and toluene, more preferably an ether solvent, benzene or toluene.
In the present invention, the reaction time is preferably 5 to 24 hours, more preferably 9 to 20 hours, and still more preferably 13 to 16 hours.
In the present invention, the reaction is preferably followed by a filtration and/or drying step, more preferably a filtration or drying step.
In the present invention, the drying means preferably includes vacuum drying.
In the present invention, the drying time is preferably 2 to 12 hours, more preferably 4 to 10 hours, and still more preferably 6 to 8 hours.
In the present invention, the drying temperature is preferably 60 to 150 ℃, more preferably 80 to 130 ℃, and still more preferably 100 to 110 ℃.
The invention relates to a complete and refined integral technical scheme, which better improves the lithium supplementing effect of a chain lithium supplementing compound serving as a lithium supplementing agent for positive electrode prelithiation, wherein the chain lithium supplementing compound specifically and preferably comprises the following contents:
a chain lithium supplementing compound of a lithium ion battery is shown as a structural formula (1):
Wherein n is more than or equal to 0 and less than or equal to 5.
Specifically, the chain lithium supplementing compound is at least one selected from the group consisting of compounds 1 to 4:
The invention also provides a synthesis method of the chain lithium supplementing compound of the lithium ion battery, which comprises the following steps: firstly, dissolving chain reactants and a lithium source in a solvent, fully reacting, filtering after generating precipitate, and finally drying in vacuum.
Specifically, the chain reactant has the structure as follows:
Wherein n is more than or equal to 0 and less than or equal to 5.
Specifically, the solvent is one of ethers (such as diethyl ether), benzene and toluene. The preferred solvent is benzene.
Specifically, the lithium source is one of lithium hydride (LiH), lithium nitride (Li 3 N) and N-butyl lithium. The preferred lithium source is n-butyllithium.
Specifically, the reaction time was 10 hours.
Specifically, the vacuum drying time was 8 hours, and the vacuum drying temperature was 90 ℃.
The invention provides a lithium ion battery, which comprises an anode, a cathode and nonaqueous lithium ion battery electrolyte;
The positive electrode contains the chain lithium supplementing compound according to any one of the above technical schemes or the chain lithium supplementing compound synthesized by the synthesis method according to any one of the above technical schemes.
In the present invention, the positive electrode preferably includes a positive electrode active material, a chain lithium supplementing compound, a conductive agent, and a binder.
In the present invention, the positive electrode active material preferably includes 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 cobalt manganate, lithium-rich manganese-based material, lithium cobalt aluminate and lithium titanate, more preferably lithium cobaltate, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, lithium vanadate, lithium manganate, lithium nickelate, lithium cobalt manganate, lithium-rich manganese-based material, lithium cobalt aluminate or lithium titanate.
In the present invention, the conductive agent preferably includes one or more of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene, and carbon nanotube, more preferably conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene, or carbon nanotube.
In the present invention, the binder preferably includes one or more of polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene, and polyhexafluoropropylene, more preferably polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene, or polyhexafluoropropylene.
In the present invention, the positive electrode preferably has a mass content of 70% to 80%, more preferably 72% to 78%, and still more preferably 74% to 76% based on the entire chain-like lithium supplementing compound, positive electrode active material, conductive agent, and binder.
In the present invention, the positive electrode preferably has a mass content of 1% to 10%, more preferably 3% to 8%, and still more preferably 5% to 6% based on the entire chain lithium supplementing compound, positive electrode active material, conductive agent, and binder.
In the present invention, the positive electrode preferably has a mass content of 1% to 10%, more preferably 3% to 8%, and still more preferably 5% to 6% based on the entire chain lithium supplementing compound, positive electrode active material, conductive agent, and binder.
In the present invention, the positive electrode preferably has a mass content of 1% to 10%, more preferably 3% to 8%, and still more preferably 5% to 6% based on the total of the chain lithium-supplementing compound, the positive electrode active material, the conductive agent, and the binder.
The invention relates to a complete and refined integral technical scheme, which better improves the lithium supplementing effect of a chain lithium supplementing compound serving as a lithium supplementing agent for positive electrode prelithiation, and the lithium ion battery specifically comprises the following components:
the lithium ion battery has a graphite cathode and a lithium iron phosphate anode, and the electrolyte contains 1MLiPF6 and EC: DMC: emc=3:5:2 (mass ratio), 5% Vinylene Carbonate (VC).
The invention provides a lithium supplementing compound, a preparation method thereof and a lithium ion battery. The invention specifically designs a chain-shaped lithium supplementing compound with a specific structure for the field of lithium ion battery prelithiation. In the structure of the chain lithium-supplementing compound, the-OLi group is used for supplementing lithium for the lithium ion battery, the-CN group is used after the chain lithium-supplementing compound supplements lithium and enters the electrolyte, and the-CN group has a strong complexing effect with transition metal in the anode material, so that a layer of film is formed on the surface of the anode of the lithium ion battery, the dissolution of transition metal ions is inhibited, and the anode is protected.
The chain lithium supplementing compound disclosed by the invention belongs to positive electrode lithium supplementing, the use method is simple, the chain lithium supplementing compound is added together with an active substance of a positive electrode material in the process of preparing slurry of a positive electrode plate, the chain lithium supplementing compound can improve the first charge-discharge specific capacity of a lithium ion battery, a product after lithium supplementing is soluble in electrolyte, and the product after lithium supplementing can be used as an electrolyte additive, so that a protective film can be formed at the positive electrode, and the cycle performance of the battery is improved. The synthesis method of the chain lithium supplementing compound provided by the invention is simple, and the lithium supplementing process is clear, and the chain lithium supplementing compound contains 3-OLi groups, so that the lithium supplementing effect is better. The lithium supplementing reaction after the power is supplied, the product after the lithium supplementing reaction has no adverse effect on the battery, and the lithium supplementing reaction can be used as an electrolyte additive.
Compared with the prior art that lithium powder or lithium foil is mainly used for supplementing lithium to the negative electrode, the method is subject to the problems that the instability of lithium, the difficulty of the process technology and the use condition are severe, the negative electrode lithium supplementing technology still cannot be applied on a large scale, and the like. Compared with the existing positive electrode lithium supplementing method, the lithium supplementing additive mainly has the defects that gas production (such as O 2, N 2 and the like) and residual metal oxide without activity can cause capacity attenuation and safety problems on the battery, and the battery needs to be sealed after the gas is completely released in the use process, so that the battery is not beneficial to various limitations such as industrial production and the like. The chain compound provided by the invention can not generate gas and have no solid substance residue in the lithium supplementing process, and the product after lithium supplementing can be dissolved in battery electrolyte, and meanwhile, the product structure contains nitrile groups, so that the chain compound can be used as an electrolyte additive for stabilizing the anode, and is beneficial to the electrochemical performance of the battery. The invention also discloses a lithium supplementing positive electrode containing the chain lithium supplementing compound and a lithium ion battery assembled by adopting the lithium supplementing positive electrode.
The experimental result shows that the first charge and discharge efficiency of the lithium ion battery assembled without adding the lithium supplementing agent is 87.48%. Active lithium loss results from the permanent consumption of Li + in the film formation of the graphite anode. The lithium ion battery after adding the positive electrode lithium supplementing agent provided by the invention has different degree of reduction in the first charge and discharge efficiency, which is caused by incapability of back intercalation after Li + in the chain-shaped lithium supplementing compound is delithiated. After the lithium supplementing agent is added, the first-time charging specific capacity and the first-time discharging specific capacity of the battery are improved to different degrees, and the lithium supplementing effect is good.
For further explanation of the present invention, the following describes a chain-shaped lithium-supplementing compound, its synthesis method and lithium ion battery in detail with reference to examples, but it should be understood that these examples are implemented on the premise of the technical scheme of the present invention, and detailed implementation and specific operation procedures are given only for further explanation of the features and advantages of the present invention, and not limitation of the claims of the present invention, and the scope of protection 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
The synthesis process of the chain lithium supplementing compound comprises the following steps:
the lithium supplementing process of the chain lithium supplementing compound is as follows:
Battery assembly
The batteries used in the embodiment and the comparative example are button batteries, the positive electrode material adopts lithium iron phosphate, and the negative electrode material adopts graphite.
Preparing a positive electrode plate: dissolving a conductive agent Super-P, an adhesive PVDF, a positive electrode active substance and a compound 1 in a solvent N-methylpyrrolidone according to a mass ratio of 2:2:89:7, uniformly mixing to prepare positive electrode slurry, uniformly coating the positive electrode slurry on a current collector aluminum foil, and drying, rolling, die cutting and drying to obtain the lithium-supplementing positive electrode plate.
Preparing a negative electrode plate: dissolving a conductive agent Super-P, a binder SBR, carboxymethyl cellulose (CMC) and graphite in deionized water according to a mass ratio of 1.5:2.3:1.5:94.7, uniformly mixing to prepare negative electrode slurry, uniformly coating the negative electrode slurry on a current collector copper foil, and drying, rolling, die cutting and drying to obtain a negative electrode plate.
And assembling the button cell by using the lithium supplementing positive pole piece, the negative pole piece, the diaphragm, the gasket and the elastic piece, and standing for 24 hours for later use.
Examples 1 to 4 and comparative example 1 were the same as example 1 except that the positive electrode sheet slurry composition ratios were as shown in table 1.
Referring to table 1, table 1 shows the composition ratios of the positive electrode sheet slurries of the examples and comparative examples provided by the present invention.
TABLE 1
Battery performance test
First effect test: the battery is charged to 4.25V under a constant current of 0.05C, then discharged to 2.5V under a constant current of 0.05C, and the first charge and discharge efficiency of the battery is observed.
The battery performance test results of the examples and comparative examples are shown in table 2.
Referring to table 2, table 2 shows the battery performance test results of the examples and comparative examples provided by the present invention.
TABLE 2
As can be seen from the battery performance test results of table 2, the first charge and discharge efficiency of the lithium ion battery assembled in the comparative example was 87.48%. Active lithium loss results from the permanent consumption of Li + in the film formation of the graphite anode. In the lithium ion batteries of examples 1 to 4, the first charge and discharge efficiencies were reduced to various degrees, namely 82.49%, 83.29%, 85.03%, and 85.23%, respectively, due to the inability to back-intercalate Li + in the chain-like lithium-compensating compound after delithiation. In the embodiment 1-2, the theoretical gram capacities of the compound 1-2 are 502mAh/g and 372mAh/g respectively, the first charge specific capacity of the battery is respectively improved by 20.42 percent (29.92 mAh/g) and 13.43 percent (19.68 mAh/g), the first discharge specific capacity is respectively improved by 13.56 percent (17.38 mAh/g) and 8.78 percent (11.25 mAh/g), and the lithium supplementing effect is better; in examples 3 and 4, theoretical gram capacities of the compounds 3 to 4 are 295.6mAh/g and 245.1mAh/g, respectively, the first charge specific capacities of the batteries are improved by 8.76% (12.83 mAh/g) and 6.54% (9.58 mAh/g), respectively, and the first discharge specific capacities are improved by 5.71% (7.32 mAh/g) and 3.79% (4.87 mAh/g), respectively, and since the gram capacities of the chain lithium-supplementing compounds of examples 3 and 4 are low, the lithium-supplementing effect is affected, the improvement of the battery capacities is limited.
Therefore, it can be concluded that the first charge-discharge specific capacity of the lithium ion battery can be improved after the chain lithium supplementing compound is added, and the electrochemical performance of the battery can be further improved.
The lithium supplementing compound, the preparation method thereof and the lithium ion battery are provided. The detailed description sets forth the principles and embodiments of the present invention using specific examples, which are presented herein to facilitate an understanding of the principles and concepts of the invention, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection 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 do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (10)
1. A chain lithium supplementing compound is characterized by having a structure shown in a formula (I):
Wherein n is the polymerization degree, and n is more than or equal to 0 and less than or equal to 5.
2. The chain lithium-supplementing compound according to claim 1, wherein the chain lithium-supplementing compound has one of structures represented by formulae (1) to (4):
3. The chain lithium-supplementing compound according to claim 1, wherein the chain lithium-supplementing compound is a positive electrode lithium-supplementing material;
The positive electrode comprises a positive electrode of a lithium ion battery;
the mass ratio of the chain lithium supplementing compound to the positive electrode active material in the positive electrode of the lithium ion battery is (1-10): (70-80).
4. A method for synthesizing the chain lithium-supplementing compound according to any one of claims 1 to 3, comprising the steps of:
1) Dissolving chain raw materials with a specific structure (II) and a lithium source in a solvent, and reacting to obtain a chain lithium supplementing compound;
Wherein n is the polymerization degree, and n is more than or equal to 0 and less than or equal to 5.
5. The synthesis method according to claim 4, wherein the molar ratio of the chain raw material to the lithium source is 1 (3.1 to 3.4);
The lithium source includes one or more of lithium hydride, lithium nitride, and n-butyllithium.
6. The synthetic method of claim 4 wherein the solvent comprises one or more of an ether solvent, benzene, and toluene;
the reaction time is 5-24 hours;
The reaction may further comprise a filtration and/or drying step.
7. The method of synthesis according to claim 6, wherein the drying means comprises vacuum drying;
the drying time is 2-12 hours;
the drying temperature is 60-150 ℃.
8. The lithium ion battery is characterized by comprising a positive electrode, a negative electrode and nonaqueous lithium ion battery electrolyte;
the positive electrode contains the chain lithium-supplementing compound according to any one of claims 1 to 3 or the chain lithium-supplementing compound synthesized by the synthesis method according to any one of claims 4 to 7.
9. The lithium ion battery of claim 8, wherein the positive electrode comprises a positive electrode active material, a chain lithium-compensating compound, a conductive agent, and a binder;
the positive electrode 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 manganate, lithium-rich manganese-based material, lithium nickel cobalt aluminate and lithium titanate;
The conductive agent comprises one or more of conductive carbon black, carbon fiber, acetylene black, ketjen black, graphene and carbon nano tubes;
the binder comprises one or more of polypropylene, polyethylene, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene and polyhexafluoropropylene.
10. The lithium ion battery according to claim 9, wherein the positive electrode is formed by integrating a chain-shaped lithium supplementing compound, a positive electrode active material, a conductive agent and a binder, and the mass content of the positive electrode active material is 70-80%;
the positive electrode is formed by taking a chain lithium supplementing compound, a positive electrode active material, a conductive agent and a binder as a whole, wherein the mass content of the conductive agent is 1% -10%;
the positive electrode is formed by taking a chain lithium supplementing compound, a positive electrode active material, a conductive agent and a binder as a whole, wherein the mass content of the binder is 1-10%;
the positive electrode is formed by taking a chain lithium supplementing compound, a positive electrode active material, a conductive agent and a binder as a whole, wherein the mass content of the chain lithium supplementing compound is 1-10%.
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