CN115548476A - Lithium-supplement positive pole piece and preparation method and application thereof - Google Patents
Lithium-supplement positive pole piece and preparation method and application thereof Download PDFInfo
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- CN115548476A CN115548476A CN202211233266.1A CN202211233266A CN115548476A CN 115548476 A CN115548476 A CN 115548476A CN 202211233266 A CN202211233266 A CN 202211233266A CN 115548476 A CN115548476 A CN 115548476A
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- lithium
- aluminosilicate
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- positive pole
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- 239000013589 supplement Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 126
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 125
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 52
- 239000000654 additive Substances 0.000 claims abstract description 48
- 230000000996 additive effect Effects 0.000 claims abstract description 44
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 38
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 37
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011149 active material Substances 0.000 claims description 27
- 239000011230 binding agent Substances 0.000 claims description 27
- 239000006258 conductive agent Substances 0.000 claims description 27
- 229960002089 ferrous chloride Drugs 0.000 claims description 20
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000011888 foil Substances 0.000 claims description 14
- 230000001502 supplementing effect Effects 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000011267 electrode slurry Substances 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 239000004277 Ferrous carbonate Substances 0.000 claims description 4
- 229910018071 Li 2 O 2 Inorganic materials 0.000 claims description 4
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 claims description 4
- SXQXMCWCWVCFPC-UHFFFAOYSA-N aluminum;potassium;dioxido(oxo)silane Chemical compound [Al+3].[K+].[O-][Si]([O-])=O.[O-][Si]([O-])=O SXQXMCWCWVCFPC-UHFFFAOYSA-N 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
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 4
- 229960004652 ferrous carbonate Drugs 0.000 claims description 4
- 235000019268 ferrous carbonate Nutrition 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910000015 iron(II) carbonate Inorganic materials 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 3
- 229910000502 Li-aluminosilicate Inorganic materials 0.000 claims description 3
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 235000012215 calcium aluminium silicate Nutrition 0.000 claims description 3
- 239000000404 calcium aluminium silicate Substances 0.000 claims description 3
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 claims description 3
- 229940078583 calcium aluminosilicate Drugs 0.000 claims description 3
- 229940046149 ferrous bromide Drugs 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000000429 sodium aluminium silicate Substances 0.000 claims description 3
- 235000012217 sodium aluminium silicate Nutrition 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 229940076136 ferrous iodide Drugs 0.000 claims description 2
- 229960001781 ferrous sulfate Drugs 0.000 claims description 2
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000007784 solid electrolyte Substances 0.000 abstract description 3
- 230000008961 swelling Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 23
- 238000004519 manufacturing process Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000005184 irreversible process Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—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
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a lithium supplement positive pole piece and a preparation method and application thereof, wherein an active layer of the lithium supplement positive pole piece comprises a lithium supplement agent and an additive; the additive includes a ferrous salt and/or an aluminosilicate. The additive in the lithium supplement positive pole piece can absorb impurity gas generated by the lithium supplement agent, and the impurity gas and HF generated in the component volume process are subjected to chemical reaction, so that the lithium supplement positive pole piece also plays a role of a catalyst, the phenomenon of battery core swelling is avoided, the safety performance of the battery is improved, the damage of an SEI (solid electrolyte interface) film on the surface of the positive/negative pole is reduced, the gram volume of the lithium supplement agent in the positive pole piece is exerted to the maximum extent, and the electrochemical performance of the battery is obviously improved.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to a lithium-supplement positive pole piece, and a preparation method and application thereof.
Background
In the first charge and discharge process of the lithium ion battery, electrolyte can be reduced and decomposed on the surface of a negative electrode material to form a solid electrolyte interface (SEI film), and the process of forming the SEI film is an irreversible process, so that the problems of reduction of lithium content, reduction of coulombic efficiency, poor cycle performance and the like can be caused, and therefore, the problems can be overcome by supplementing lithium ions into the battery.
The lithium supplementing technology is mainly divided into positive electrode lithium supplementing and negative electrode lithium supplementing, the negative electrode lithium supplementing mainly comprises lithium foil lithium supplementing and lithium powder lithium supplementing, but the lithium metal is more active, so that the requirements on storage and manufacturing environments are higher, greater safety risks and complex processing risks exist, and the production cost is higher. Compared with the difficult and high-input negative electrode lithium supplement, the positive electrode lithium supplement technology has attracted much attention due to high safety and simple production process, and the typical positive electrode lithium supplement is to supplement the irreversible capacity loss of the first charge and discharge by adding a small amount of high-capacity material in the positive electrode slurry mixing process.
At present, the material of the common positive electrode lithium supplement additive mainly comprises a lithium-rich compound (Li) 2 NiO 2 、Li 5 FeO 4 ) And binary lithium compounds (Li) 3 N、Li 2 O 2 ) (ii) a For a conventional lithium iron phosphate battery cell, after the lithium supplement agent is added, a lithium source consumed by forming an SEI film in the first charging can be compensated, so that the capacity, the energy density and the cycle performance of the battery are improved to a certain extent. However, the conventional lithium supplement agent described above is very reactive with moisture and carbon dioxide in the air to generate a large amount of gas, such as O 2 、CO 2 And the phenomenon is obvious in the formation stage, so that the cell is expanded and broken due to the expansion, and the safety problem is caused.
In order to solve the above problems, the prior art performs related optimization and improvement on a lithium supplement system battery cell from the following aspects: (1) Coating LiCoO on the surface of the positive electrode lithium supplement agent 2 、Li 2 MoO 3 、Mo 2 N、ZrO 2 Or activated carbon, etc. to stabilize the structure of the lithium supplementing agent and slow down the reaction between the lithium supplementing agent and airCarrying out a reaction; (2) Under the environment with certain humidity, the positive electrode lithium supplement agent, water and carbon dioxide generate stable lithium carbonate on the surface of the positive electrode lithium supplement agent, and the reaction of the water and the inner layer lithium supplement agent is isolated; (3) prolonging the formation air extraction time; however, the first and second methods only slow down the reaction between the positive electrode lithium supplement agent and air, and cannot solve the problem of large amount of gas generation after the lithium removal of the positive electrode lithium supplement agent in the formation stage, and the third method is not favorable for the production efficiency of a factory, and the incomplete gas removal is easy to cause the problem of interface brown spots.
Based on the research, a lithium supplement positive pole piece is needed to be provided, and the lithium supplement positive pole piece can not only compensate a lithium source consumed by the SEI film formed by first charging, but also solve the problems of battery over-thickness, bulging and thermal runaway caused by gas production of a lithium supplement system, and the problem that the SEI film is damaged in a formation process.
Disclosure of Invention
The invention aims to provide a lithium supplement positive pole piece and a preparation method and application thereof, wherein the lithium supplement positive pole piece comprises a lithium supplement agent for supplementing lithium and an additive, so that the lithium supplement positive pole piece not only can supplement lithium, but also avoids the phenomenon of battery core bulge, reduces potential safety hazards, eliminates the influence of the lithium supplement agent on an SEI film in a formation process, and enables the lithium supplement agent to obtain maximum gram capacity exertion.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a lithium supplement positive electrode plate, wherein an active layer of the lithium supplement positive electrode plate comprises a lithium supplement agent and an additive;
the additive comprises a ferrous salt and/or an aluminosilicate.
The additive added into the active layer can solve the problems that the lithium supplement agent is unstable to generate gas and an SEI film is damaged in the formation process, wherein the lithium supplement agent is unstable and can react with moisture in the air to generate oxygen and carbon dioxide, the ferrous salt can react with the oxygen to absorb oxygen serving as an impurity, and aluminosilicate can react with CO serving as a gas impurity to absorb oxygen serving as an impurity 2 Reaction, therefore, the existence of the additive avoids the phenomenon of cell bulging, and reduces the safetyHidden danger; on the other hand, the aluminosilicate can chemically react with HF generated in the chemical composition and volume process, so that the damage of an SEI (solid electrolyte interphase) film on the surface of the positive/negative electrode is reduced, and meanwhile, the aluminosilicate can also play a role of a catalyst, so that the lithium supplement in the positive plate is exerted to the maximum gram capacity.
Preferably, the additives are ferrous salts and aluminosilicates.
The ferrous salt and the aluminum silicate have a synergistic effect, and because the ferrous salt and the aluminum silicate simultaneously can respectively absorb oxygen and carbon dioxide generated by the lithium supplement agent, impurity gases generated by the lithium supplement agent can be absorbed to the greatest extent, and potential safety hazards caused by thermal runaway are avoided.
Preferably, the aluminosilicate has the formula M x O y ·Al 2 O 3 ·SiO 2 Where M comprises any one or a combination of at least two of Na, K, mg, ca or Fe, the values of x and y are adapted to the type of M, preferably 0 < x < 2.5, and may be, for example, 1, 1.5 or 2,0 < y < 3, such as 1, 1.5 or 3, but not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preferably, the ferrous salt and aluminosilicate are present in a mass ratio of (1-4): 6-9, and may be, for example, 1:6, 2:7, 3:8 or 4:9, but are not limited to the values recited, and other values not recited in the numerical ranges are equally applicable.
Compared with ferrous salt, the aluminosilicate provided by the invention is excessive, because the aluminum silicate not only plays a role of absorbing impurity gas, but also reacts with HF and is also used as a catalyst, if the aluminum silicate is too little, the effect cannot be effectively played, if the addition amount of the aluminum silicate is too much, the relative ferrous salt is too little, the synergistic effect between the ferrous salt and the aluminosilicate can be destroyed, therefore, under the condition that the total amount of the additive is not changed, the mass ratio of the ferrous salt and the aluminosilicate is within a reasonable range, the synergistic effect can be played, the corresponding effect is achieved, otherwise, the gas yield of the battery is increased, the capacity is reduced and the cycle performance is reduced.
Preferably, the active layer further includes an active material, a binder, and a conductive agent.
Preferably, the additive is present in an amount of 0.02 to 0.1wt%, such as 0.02wt%, 0.03wt%, 0.04wt%, 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt%, or 0.1wt%, based on the total mass of the active material, binder, and conductive agent, but not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
The additive content of the invention should be in a reasonable range to exert the effect, if the additive content is too low, the gas production cannot be effectively reduced, and simultaneously the capacity is reduced and the cycle performance is reduced; if the addition amount is too large, the gram capacity of the electrode sheet is affected, and the battery performance is degraded.
Preferably, the ferrous salt comprises any one of ferrous chloride, ferrous sulfate, ferrous carbonate, ferrous bromide, or ferrous iodide, or a combination of at least two thereof, and typical, but not limiting, combinations include a combination of ferrous chloride and ferrous sulfate, or a combination of ferrous carbonate and ferrous bromide, preferably ferrous chloride.
The ferrous salt is preferably ferrous chloride, and because the ferrous chloride cannot introduce other ions into the positive electrode system and influence the normal exertion of the positive electrode performance due to the addition of the ferrous chloride, the lithium iron phosphate system has higher adaptation degree and the obtained battery has better performance.
Preferably, the aluminosilicate comprises any one or a combination of at least two of sodium aluminosilicate, lithium aluminosilicate, potassium aluminosilicate, magnesium aluminosilicate, iron aluminosilicate or calcium aluminosilicate, typical but not limiting combinations include sodium aluminosilicate and lithium aluminosilicate, potassium aluminosilicate and magnesium aluminosilicate, or iron aluminosilicate and calcium aluminosilicate, preferably iron aluminosilicate.
The aluminosilicate of the present invention is preferably iron aluminosilicate as it also does not introduce other species of ions into the anode system.
Preferably, the particle diameter D50 of the lithium-supplementing agent is 4 to 10 μm, and may be, for example, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
When the particle size D50 of the lithium supplement agent is too small, the surface activity of the lithium supplement agent is too strong, the risks of strong water absorption, quick change of slurry viscosity, large gas production and the like exist, and when the particle size D50 of the positive electrode lithium supplement agent is too large, the activity is weaker, and the improvement effect on the system capacity and the cycle performance is poorer.
Preferably, the lithium supplementing agent is present in an amount of 0.2 to 0.5 wt.%, based on the mass of the active layer, and may be, for example, 0.2 wt.%, 0.25 wt.%, 0.3 wt.%, 0.35 wt.%, 0.4 wt.%, 0.45 wt.%, or 0.5 wt.%, but is not limited to the recited values, and other values not recited within the numerical ranges are equally applicable.
Preferably, the lithium supplement agent comprises a lithium-rich compound and/or a binary lithiate.
Preferably, the lithium-rich compound comprises Li 2 NiO 2 And/or Li 5 FeO 4 。
Preferably, the binary lithiate comprises Li 3 N and/or Li 2 O 2 。
Preferably, the active material is present in an amount of 90 to 95wt%, for example 90wt%, 91wt%, 92wt%, 93wt%, 94wt% or 95wt%, based on the mass of the active layer, but is not limited to the recited values, and other values not recited within the numerical range are equally applicable.
Preferably, the binder is present in an amount of 1 to 2 wt.%, based on the mass of the active layer, and may be, for example, 1 wt.%, 1.2 wt.%, 1.4 wt.%, 1.5 wt.%, 1.7 wt.%, 1.9 wt.%, or 2 wt.%, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the conductive agent is present in an amount of 3 to 4wt%, for example 3wt%, 3.2wt%, 3.4wt%, 3.6wt%, 3.8wt% or 4wt%, based on the mass of the active layer, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the active material comprises any one of lithium iron phosphate, lithium cobaltate, lithium manganate or ternary materials or a combination of at least two of the foregoing, and typical but non-limiting combinations include a combination of lithium iron phosphate and lithium cobaltate, or a combination of lithium manganate and ternary materials.
Preferably, the binder comprises any one or a combination of at least two of polyvinylidene fluoride, styrene butadiene rubber or polyvinyl alcohol, and typical but non-limiting combinations include a combination of polyvinylidene fluoride and styrene butadiene rubber, or a combination of polyvinyl alcohol and polyvinylidene fluoride.
Preferably, the conductive agent comprises any one of or a combination of at least two of conductive carbon black, conductive graphite, conductive carbon nanotubes, or graphene, with typical but non-limiting combinations comprising a combination of conductive carbon black and conductive graphite, or a combination of conductive carbon nanotubes and graphene.
In a second aspect, the invention provides a method for preparing the lithium-supplement positive electrode plate, which comprises the following steps:
mixing an active material, a binder, a conductive agent, a lithium supplement agent and an additive according to the formula amount, preparing the obtained mixture into positive electrode slurry, and coating to obtain the lithium supplement positive electrode piece.
The preparation method adopted by the invention does not carry out operations such as coating or doping, and only needs to add the additive directly in the anode homogenizing process, and also does not carry out modification such as coating on the lithium supplement agent, so that the preparation method is simple and easy to operate, has low cost, can be applied in large scale in industry,
preferably, the coated foil comprises an aluminum foil;
preferably, the preparation method further comprises the steps of drying, cold pressing and die cutting of the strips after coating.
In a third aspect, the present invention provides a lithium ion battery, including the lithium supplement positive electrode plate described in the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the additive is added into the lithium supplement positive pole piece, so that impurity gas generated by the lithium supplement agent can be absorbed, the phenomenon of battery core swelling is avoided, the safety performance is improved, the additive can also perform chemical reaction with HF generated in the formation and grading process, the damage of an SEI film on the surface of a positive/negative pole is reduced, the electrochemical performance of the battery is improved, and meanwhile, the additive also plays a role of a catalyst, so that the lithium supplement agent in the positive pole piece can be exerted to the maximum gram capacity; in addition, the preparation method of the lithium supplement anode piece is simple and convenient, the cost is low, the lithium supplement agent and the additive are added in the anode homogenizing process, and the modification operation of the lithium supplement agent is not needed, so that the lithium supplement anode piece can be industrially applied in a large scale.
Drawings
FIG. 1 is a disassembled interface diagram of a battery manufactured by the lithium-supplementing positive electrode plate in example 1 of the present invention;
FIG. 2 is an interface diagram of a disassembled battery prepared by the lithium-supplement positive pole piece in comparative example 1 of the invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a lithium supplement positive pole piece, which comprises an aluminum foil and active layers on the surfaces of two sides of the aluminum foil, wherein the active layers comprise active materials, conductive agents, binders, lithium supplement agents and additives;
the additive is ferrous chloride and ferric aluminosilicate (Fe) 2 O 3 ·Al 2 O 3 ·SiO 2 ) The mass ratio of the ferrous chloride to the ferric aluminosilicate is 3:7; the content of the additive accounts for 0.06wt% of the total mass of the active material, the binder and the conductive agent;
the content of the lithium supplement agent is 0.4wt% based on the mass of the active layer, and the lithium supplement agent is Li 2 NiO 2 The particle size D50 is 6 μm;
based on the mass of the active layer, the content of the active material is 94.5wt%, the content of the binder is 1.5wt%, the content of the conductive agent is 3.5wt%, the active material is lithium iron phosphate, the binder is polyvinylidene fluoride, and the conductive agent is conductive carbon black;
the preparation method of the lithium-supplement positive pole piece comprises the following steps:
mixing an active material, a binder, a conductive agent, a lithium supplement agent and an additive according to a formula amount, adding N-methyl pyrrolidone to prepare a mixture into positive electrode slurry, coating the positive electrode slurry on two sides of an aluminum foil, and drying, cold-pressing and die-cutting to obtain the lithium supplement positive electrode piece;
the interface diagram of the disassembled battery made of the lithium-supplement positive pole piece is shown in figure 1.
Example 2
The embodiment provides a lithium supplement positive pole piece, which comprises an aluminum foil and active layers on the surfaces of two sides of the aluminum foil, wherein the active layers comprise active materials, conductive agents, binders, lithium supplement agents and additives;
the additive is ferrous chloride and ferric aluminosilicate, and the mass ratio of the ferrous chloride to the ferric aluminosilicate is 1:6; the content of the additive accounts for 0.02wt% of the total mass of the active material, the binder and the conductive agent;
the content of the lithium supplement agent is 0.5wt% based on the mass of the active layer, and the lithium supplement agent is Li 3 N, the particle size D50 is 10 μm;
based on the mass of the active layer, the content of the active material is 94wt%, the content of the binder is 2wt%, the content of the conductive agent is 3wt%, the active material is lithium iron phosphate, the binder is styrene butadiene rubber, and the conductive agent is a conductive carbon nano tube;
the preparation method of the lithium-supplement positive pole piece comprises the following steps:
mixing an active material, a binder, a conductive agent, a lithium supplement agent and an additive according to the formula amount, adding N-methyl pyrrolidone to prepare a mixture into positive electrode slurry, coating the positive electrode slurry on two sides of an aluminum foil, and drying, cold-pressing and die-cutting to obtain the lithium supplement positive electrode piece.
Example 3
The embodiment provides a lithium supplement positive pole piece, which comprises an aluminum foil and active layers on the surfaces of two sides of the aluminum foil, wherein the active layers comprise active materials, conductive agents, binders, lithium supplement agents and additives;
the additive is ferrous chloride and ferric aluminosilicate, and the mass ratio of the ferrous chloride to the ferric aluminosilicate is 4:9; the content of the additive accounts for 0.1wt% of the total mass of the active material, the binder and the conductive agent;
the content of the lithium supplement agent is 0.2wt% based on the mass of the active layer, and the lithium supplement agent is Li 2 O 2 The particle size D50 is 4 μm;
based on the mass of the active layer, the content of the active material is 93wt%, the content of the binder is 2wt%, the content of the conductive agent is 4wt%, the active material is lithium manganate, the binder is styrene butadiene rubber, and the conductive agent is graphene;
the preparation method of the lithium-supplement positive pole piece comprises the following steps:
mixing an active material, a binder, a conductive agent, a lithium supplement agent and an additive according to the formula amount, adding N-methyl pyrrolidone to prepare a mixture into positive electrode slurry, coating the positive electrode slurry on two sides of an aluminum foil, and drying, cold-pressing and die-cutting to obtain the lithium supplement positive electrode piece.
Example 4
This example provides a lithium-supplemented positive electrode sheet, which is the same as example 1 except that ferrous chloride and other qualities are replaced by ferrous sulfate.
Example 5
This example provides a lithium-supplemented positive electrode sheet, which is the same as example 1 except that ferrous chloride or the like is replaced by ferrous carbonate.
Example 6
This example provides a lithium-supplemented positive electrode sheet, which is prepared by replacing the quality of ferric aluminosilicate with magnesium aluminosilicate (MgO — Al) 2 O 3 ·SiO 2 ) Otherwise, the same procedure as in example 1 was repeated.
Example 7
The embodiment provides a lithium supplement positive pole piece, which replaces the quality of iron aluminosilicate and the likeIs replaced by potassium aluminosilicate (K) 2 O·Al 2 O 3 ·SiO 2 ) Otherwise, the same procedure as in example 1 was repeated.
Example 8
The present embodiment provides a lithium supplement positive electrode piece, which is the same as in embodiment 1 except that the mass ratio of the ferrous chloride to the ferric aluminosilicate is 3:5.
Example 9
The embodiment provides a lithium supplement positive pole piece, which is the same as the lithium supplement positive pole piece in the embodiment 1 except that the mass ratio of the ferrous chloride to the ferric aluminosilicate is 3.
Example 10
The embodiment provides a lithium supplement positive pole piece, which is the same as the lithium supplement positive pole piece in the embodiment 1 except that the content of the additive accounts for 0.01wt% of the total mass of the active material, the binder and the conductive agent.
Example 11
The embodiment provides a lithium supplement positive pole piece, which is the same as the lithium supplement positive pole piece in the embodiment 1 except that the content of the additive accounts for 0.15wt% of the total mass of the active material, the binder and the conductive agent.
Example 12
The embodiment provides a lithium supplement positive electrode piece, which is the same as that in embodiment 1 except that the additive is ferrous chloride and does not include ferric aluminosilicate.
Example 13
The embodiment provides a lithium supplement positive electrode piece, which is the same as in embodiment 1 except that the additive is ferric aluminosilicate and ferrous chloride is not included.
Comparative example 1
The embodiment provides a lithium supplement positive pole piece, and the rest of the lithium supplement positive pole piece is the same as that in the embodiment 1 except that the lithium supplement positive pole piece does not contain an additive;
the interface diagram of the disassembled battery made of the lithium-supplement positive pole piece is shown in figure 2.
Comparative example 2
This example provides a positive electrode sheet, which is the same as example 1 except that it does not include a lithium replenishing agent and an additive.
The positive pole piece, the negative pole piece and the PP diaphragm are wound to prepare a winding core, the winding core is placed in an aluminum shell, electrolyte is injected into a battery cell under the negative pressure condition, and the subsequent procedures of packaging, formation, capacity grading and the like are carried out after the battery cell is fully static to obtain the lithium ion battery; the preparation method of the negative pole piece comprises the following steps: uniformly mixing a graphite material, conductive carbon black and styrene butadiene rubber in a mass ratio of 95; the electrolyte comprises 1mol of LiPF 6 As the lithium salt, EC/DC/EMC (volume ratio 1.
The prepared lithium ion battery tests the volume of produced gas, the rated capacity and the capacity retention rate after 100 cycles; the method for testing the gas production volume comprises the following steps: each example and comparative example of the lithium ion battery prepared above were subjected to parallel experiments with 3 groups, gas generation volume was measured by a drainage method, the tab of the battery was sealed with an insulating tape, 1 group of the battery (1 #) was wound with the insulating tape, the battery was immersed in water with the same hand tension, the tab of the battery was kept level with the horizontal plane, weight was recorded after the balance was stabilized, and parallel experiments with two other groups (2 # and 3 #) were performed according to the above method to obtain the exhaust volumes of the 1#,2# and 3# groups, and the average exhaust volumes of the three groups are shown in table 1; the test conditions for the calibration capacity are as follows: controlling the temperature to be 25 +/-2 ℃, carrying out charge-discharge test at 0.5C multiplying power, circulating for 10 circles, and taking the average value of the discharge capacity of the last 3 circles as a calibration capacity; the test conditions for capacity retention rate of 100 cycles are as follows: the temperature was controlled to 25 ± 2 ℃, charge and discharge tests were performed at 0.5C rate, the cycle was 100 cycles, the capacity retention rate = 100 th cycle discharge capacity/first cycle discharge capacity, and the test results are shown in table 1.
TABLE 1
From table 1, the following points can be seen:
(1) The battery prepared by the lithium supplement positive plate provided by the invention has the advantages that the drainage volume is small, the gas production rate of the battery is small, the calibration capacity is high, the cycle performance is good, the gas production rate of the battery can be obviously reduced due to the existence of the additive, and the electrochemical performance of the battery is improved; as can be seen from examples 1 and 4 to 7, the preferred ferrous salt is ferrous chloride, and the preferred aluminosilicate is iron aluminosilicate, so that the lithium iron phosphate positive electrode system can be more suitably adapted to exert a coordinating effect; from the embodiment 1 and the embodiments 9 to 12, it can be known that the content of the additive and the mass ratio of the ferrous salt to the aluminosilicate are within a reasonable range, so that the gas production can be further reduced, and the performance can be improved; it can be seen from the examples 1 and 13 to 14 that the ferrous salt and the aluminosilicate exert different functions, and the combined use of the ferrous salt and the aluminosilicate can simultaneously solve the problems of gas generation and SEI film damage, thereby reducing the gas generation amount to the maximum extent and improving the electrochemical performance.
(2) It can be known from the example 1 and the comparative example 1 that the gas production rate is obviously increased and the calibration capacity and the cycle performance are reduced because no additive is added in the comparative example 1, and in addition, as can be seen from comparison between the figure 1 and the figure 2, the gas production rate of the battery is more because no additive is added, so that the black spots appear on the interface, but the invention can avoid the occurrence of the black spots through the addition of the additive, so as to ensure the safety performance of the battery; it is understood from example 1 and comparative example 2 that the performance of the battery is further degraded when neither the lithium supplementing agent nor the additive is added.
In conclusion, according to the lithium supplement positive pole piece and the preparation method and application thereof provided by the invention, the lithium supplement positive pole piece can not only make up the lithium source consumed by the SEI film formed by first charging, but also solve the problems of battery over-thickness, bulging and thermal runaway caused by gas production of a lithium supplement system and the problem of SEI film damage in the formation process.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. The lithium supplement positive pole piece is characterized in that an active layer of the lithium supplement positive pole piece comprises a lithium supplement agent and an additive;
the additive includes a ferrous salt and/or an aluminosilicate.
2. The lithium-supplementing positive pole piece of claim 1, wherein the mass ratio of the ferrous salt to the aluminosilicate is (1-4) to (6-9);
preferably, the active layer further includes an active material, a binder, and a conductive agent;
preferably, the additive is contained in an amount of 0.02 to 0.1wt% based on the total mass of the active material, the binder and the conductive agent.
3. The lithium-supplementing positive pole piece according to claim 1 or 2, wherein the ferrous salt comprises any one of or a combination of at least two of ferrous chloride, ferrous sulfate, ferrous carbonate, ferrous bromide or ferrous iodide;
preferably, the aluminosilicate comprises any one of, or a combination of at least two of, sodium aluminosilicate, lithium aluminosilicate, potassium aluminosilicate, magnesium aluminosilicate, iron aluminosilicate, or calcium aluminosilicate.
4. The lithium supplement positive pole piece according to any one of claims 1 to 3, wherein the particle size D50 of the lithium supplement agent is 4 to 10 μm;
preferably, the content of the lithium supplement agent is 0.2 to 0.5wt% based on the mass of the active layer.
5. The lithium supplementing positive electrode plate according to any one of claims 1 to 4, wherein the lithium supplementing agent comprises a lithium-rich compound and/or a binary lithiate;
preferably, the lithium-rich compound comprises Li 2 NiO 2 And/or Li 5 FeO 4 ；
Preferably, the binary lithiate comprises Li 3 N and/or Li 2 O 2 。
6. The lithium-supplementing positive electrode sheet according to any one of claims 2 to 5, wherein the content of the active material is 90 to 95wt% based on the mass of the active layer;
preferably, the binder is present in an amount of 1-2wt%, based on the mass of the active layer;
preferably, the content of the conductive agent is 3 to 4wt% based on the mass of the active layer.
7. The lithium-supplementing positive electrode plate according to any one of claims 2 to 6, wherein the active material comprises any one of lithium iron phosphate, lithium cobaltate, lithium manganate or ternary materials or a combination of at least two of the materials;
preferably, the binder comprises any one or a combination of at least two of polyvinylidene fluoride, styrene butadiene rubber or polyvinyl alcohol;
preferably, the conductive agent comprises any one of or a combination of at least two of conductive carbon black, conductive graphite, conductive carbon nanotubes or graphene.
8. The preparation method of the lithium-supplementing positive pole piece according to any one of claims 1 to 7, characterized by comprising the following steps:
mixing an active material, a binder, a conductive agent, a lithium supplement agent and an additive according to the formula amount, preparing the obtained mixture into positive electrode slurry, and coating to obtain the lithium supplement positive electrode piece.
9. The method of claim 8, wherein the coated foil comprises aluminum foil;
preferably, the preparation method further comprises the steps of drying, cold pressing and die cutting of the strips after coating.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the lithium-supplementing positive electrode sheet according to any one of claims 1 to 7.
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| CN116344978B (en) * | 2023-05-29 | 2023-08-04 | 江苏正力新能电池技术有限公司 | Positive electrode plate and application thereof |
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