CN112164796A - Pre-lithiation additive for positive electrode material of lithium ion battery and preparation method and application thereof - Google Patents
Pre-lithiation additive for positive electrode material of lithium ion battery and preparation method and application thereof Download PDFInfo
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- 239000000654 additive Substances 0.000 title claims abstract description 43
- 230000000996 additive effect Effects 0.000 title claims abstract description 43
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 title claims description 24
- 238000006138 lithiation reaction Methods 0.000 title description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910010699 Li5FeO4 Inorganic materials 0.000 claims abstract description 28
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000010405 anode material Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 229910032387 LiCoO2 Inorganic materials 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 14
- 239000006258 conductive agent Substances 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 2
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 229910012820 LiCoO Inorganic materials 0.000 abstract description 6
- 239000011149 active material Substances 0.000 abstract description 3
- 230000009849 deactivation Effects 0.000 abstract description 3
- 229910012923 LiCoO2In Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 230000002427 irreversible effect Effects 0.000 description 6
- 239000013589 supplement Substances 0.000 description 5
- 238000005056 compaction Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a prelithiation additive of a lithium ion battery anode material and a preparation method and application thereof, relating to the technical field of preparation of the lithium ion battery anode material2F doped with Li5FeO4(ii) a The preparation method comprises the steps of mixing an iron source, a lithium source, a fluorine source, a complexing agent and deionized water, stirring for reaction to obtain sol, continuing stirring for reaction, drying and grinding to obtain precursor powder, presintering and cooling to obtain F-doped Li5FeO4Then it is mixed with nano-grade Co3O4Mixing with lithium source, calcining to obtain surface-coated LiCoO2F doped with Li5FeO4The prelithiation additive of (a). The prelithiation additive of the invention, Li5FeO4Is doped with F element and is coated with LiCoO on the surface2Can stabilize the material Li5FeO4The structure of (1) slows down the reaction between the air and the water; simultaneous LiCoO2In a layered structure, Li may be allowed to exist5FeO4Li in (1)+Free to deintercalate, LiCoO after deactivation of the prelithiation additive when the first charge is over2Still active and does not block Li in the active material+To be transmitted.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery anode materials, in particular to a prelithiation additive of a lithium ion battery anode material, and a preparation method and application thereof.
Background
Since Li is generated during the first charging process of the lithium ion battery+When the lithium ion battery is extracted from the positive electrode and inserted into the negative electrode material, an SEI (solid electrolyte film) is formed on the surface of the negative electrode, so that a part of active Li is consumed+And this part of the lost Li+So called irreversible capacity loss, and therefore, the application of the lithium supplement process is particularly urgent for improving the first charge-discharge efficiency. At present, the most common lithium supplementing process is a negative electrode lithium supplementing method, namely, processes such as lithium powder and lithium foil are adopted to supplement irreversible capacity loss of a negative electrode in the first charging process, and in addition, another lithium supplementing method under research is a positive electrode lithium supplementing process, namely, a small amount of high-capacity lithium-containing oxide including a lithium-rich compound, a nano composite material based on conversion reaction, a binary lithium compound and the like is added to a positive electrode. Compared with the cathode lithium supplement with high difficulty and high investment, the anode lithium supplement is much simpler.
In the prior art, a small amount of Li which is a high-lithium-rich material is added in the slurry mixing process5FeO4The prelithiation additive used as the anode material of the lithium ion battery has very high theoretical capacity, the theoretical specific capacity can reach 700mAh/g, and almost all the additiveSome capacities are irreversible, the materials are quickly inactivated after lithium removal is finished, do not participate in charge-discharge reaction any more, and the loss of irreversible capacity can be supplemented in the first charge-discharge process; however, since it is unstable in air, it needs to be stored and used in an inert atmosphere; and when Li5FeO4Deactivation after delithiation can affect Li in the battery+And further affects battery capacity and charge-discharge rate.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a prelithiation additive of a lithium ion battery anode material, a preparation method and application thereof, wherein the prelithiation additive Li5FeO4Is doped with F element and is coated with LiCoO on the surface2On the one hand, the material Li can be stabilized5FeO4On the other hand, Li may be used5FeO4Li in (1)+Free to deintercalate and does not hinder Li in the active material after deactivation of the prelithiation additive when first charge is terminated+To be transmitted.
The invention provides a prelithiation additive of a lithium ion battery anode material, which is surface-coated with LiCoO2F doped with Li5FeO4。
In the present invention, the prelithiation additive is surface coated LiCoO2F doped Li5FeO4May be abbreviated as LiCoO2@Li5FeO4-xFx(0≤x≤4)。
The invention also provides a preparation method of the pre-lithiation additive for the lithium ion battery anode material, which comprises the following steps:
s1, mixing an iron source, a lithium source, a fluorine source, a complexing agent and deionized water, stirring for reaction to obtain sol, continuing stirring for reaction, drying and grinding to obtain precursor powder, presintering and cooling to obtain F-doped Li5FeO4；
S2, F-doped Li5FeO4And nano-scale Co3O4Mixing with lithium source, calcining to obtain surface-coated LiCoO2F doped with Li5FeO4The prelithiation additive of (a).
Preferably, in S1, stirring and reacting for 3h after obtaining the sol, heating and drying for 12h at 60 ℃, and grinding to obtain precursor powder; preferably, the pre-sintering is performed at 300-600 ℃ for 5-8 h.
Preferably, the iron source is one or more of ferric nitrate, ferric sulfate and ferric chloride; the lithium source is one or more of lithium hydroxide, lithium carbonate or lithium acetate; the fluorine source is ammonium fluoride; the complexing agent is oxalic acid.
Preferably, in S1, the mass ratio of the iron source, the lithium source, the fluorine source, the complexing agent and the deionized water is 50-200: 25-300: 10-100: 5-100: 250 to 1000 parts; wherein the molar ratio of Fe element in the iron source to Li element in the lithium source is 1: 5 to 8.
Preferably, in S2, nanoscale Co3O4The molar ratio of the medium Co element to the Li element in the lithium source is 1: 1 to 1.2; preferably, nanoscale Co3O4Li doped with F5FeO4The mass ratio of (A) to (B) is 1-50: 1000, parts by weight; preferably, nanoscale Co3O4Has a particle diameter of 50 to 500 nm.
Preferably, in S2, the calcination is performed by pre-burning at 300-500 ℃ for 3-8 h, then heating to 700-900 ℃ and calcining for 8-15 h, wherein the heating rate is 2 ℃/min.
The invention also provides the application of the pre-lithiation additive of the lithium ion battery anode material, which is to mix the pre-lithiation additive, the anode material, the conductive agent and the binder to prepare slurry, coat the slurry on a current collector, and prepare a pre-lithiated lithium ion battery anode piece through drying, rolling and drying.
Preferably, in S3, the positive electrode material is a ternary lithium nickel cobalt manganese oxide positive electrode material LiNixCoyMn1-x-yO2(x is more than or equal to 0 and less than or equal to 1); the conductive agent is one or more of carbon black, acetylene black, carbon nano tubes and graphene; the binder is PVDF.
Preferably, the mass ratio of the pre-lithiation additive to the positive electrode material to the conductive agent to the binder is 0.5-10: 70-97.5: 1-10: 1-10% and the solid content of the slurry is 50-70%.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:
1. the invention adopts the compound Li with high lithium content5FeO4As the lithium supplement additive of the lithium ion battery anode material has very high theoretical capacity, the theoretical specific capacity can reach 700mAh/g, almost all the capacity is irreversible, the material is rapidly inactivated after lithium removal is completed, and does not participate in charge-discharge reaction any more, so the loss of the irreversible capacity in the first charge-discharge process can be compensated.
2. Prelithiation additive Li prepared in the present invention5FeO4Is doped with F element and is coated with LiCoO on the surface2Can stabilize the material Li5FeO4The structure of (1) slows down the reaction between the air and the water; simultaneous LiCoO2In a layered structure, Li may be allowed to exist5FeO4Li in (1)+Free to deintercalate, LiCoO after deactivation of the prelithiation additive when the first charge is over2Still active and does not block Li in the active material+The transmission of (1); in addition, the active ternary material is reacted with LiCoO2@Li5FeO4-xFxThe blending belongs to the blending of large and small particles, so that the compaction density can be improved, and the battery capacity can be improved.
3. The prelithiation additive LiCoO of the present invention2@Li5FeO4-xFxThe preparation method has the advantages of simple preparation, abundant raw materials, low energy consumption, safe and reliable production process, low production cost and easy large-scale production.
Drawings
FIG. 1 is a graph of the rate at 0.2C, 0.33C, 1C, 0.2C return and 1C for cells prepared in example 1 of the present invention and comparative examples 1-2;
fig. 2 is a graph showing 50 cycles at 1C for the batteries prepared in example 1 of the present invention and comparative examples 1-2.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
S1, mixing ferric nitrate, lithium hydroxide, ammonium fluoride, oxalic acid and deionized water according to a mass ratio of 80: 70: 10: 7: 250, stirring and reacting to obtain sol, continuously stirring for 3h, heating and drying at 60 ℃ for 12h, grinding to obtain dry precursor powder, then raising the temperature from room temperature to 500 ℃ at the speed of 2 ℃/min for presintering for 5h, and cooling along with the furnace to obtain F-doped Li5FeO4；
S2, F-doped Li5FeO4Mixing with nanometer cobaltosic oxide and lithium hydroxide, calcining, preburning at 500 deg.C for 5 hr, further heating to 800 deg.C, sintering for 12 hr, and furnace cooling to obtain surface-coated LiCoO2F doped with Li5FeO4The prelithiation additive of (a); wherein, the molar ratio of Co element in the nanometer cobaltosic oxide to Li element in the lithium source is 1: 1.05, nanoscale Cobaltosic oxide with F-doped Li5FeO4The mass ratio of (A) to (B) is 5: 1000, parts by weight;
s3, and the prelithiation additive and the positive electrode material LiNi prepared in S20.8Co0.1Mn0.1O2The conductive agent carbon black and the binder PVDF are mixed according to the mass ratio of 5: 93: 1: 1, preparing slurry by mixing, controlling the solid content of the slurry to be 66%, then coating the slurry on an aluminum foil current collector, drying, rolling, and drying in vacuum at 80 ℃ for 12 hours to obtain the lithium ion battery positive pole piece, wherein the compaction density of the pole piece is controlled to be 3.2g/cm3。
Example 2
Compared with example 1, the difference is that:
in S1, the mass ratio of ferric nitrate, lithium hydroxide, ammonium fluoride, oxalic acid and deionized water is 200: 280: 50: 15: 800; presintering at 300 ℃ for 8h, and cooling with a furnace to obtain F-doped Li5FeO4；
In S2, the molar ratio of Co element in nano cobaltosic oxide to Li element in lithium source is 1: 1.1; nano-scale cobaltosic oxide and F-doped Li5FeO4The mass ratio of (1): 100, respectively;
in S3, the prelithiation additive and the positive electrode material LiNi0.8Co0.1Mn0.1O2Conductive agent carbonThe mass ratio of the black to the PVDF binder is 6.5: 91: 1: 1.5, mixing to prepare slurry; controlling the compacted density to be 3.1g/cm3。
The rest is the same as in example 1.
Example 3
Compared with example 1, the difference is that:
in S1, the mass ratio of ferric nitrate, lithium hydroxide, ammonium fluoride, oxalic acid and deionized water is 200: 280: 50: 15: 800;
in S2, the calcination is to presintered for 5h at 500 ℃, and then the temperature is continuously raised to 860 ℃ for sintering for 10 h; the molar ratio of Co element in the nano cobaltosic oxide to Li element in the lithium source is 1: 1.15; nano-scale cobaltosic oxide and F-doped Li5FeO4The mass ratio of (A) to (B) is 3: 100, respectively;
in S3, the prelithiation additive and the positive electrode material LiNi0.8Co0.1Mn0.1O2The conductive agent carbon black and the binder PVDF are mixed according to the mass ratio of 5: 93: 1: 1, mixing to prepare slurry; controlling the compacted density to be 3.2g/cm3。
The rest is the same as in example 1.
Example 4
Compared with example 1, the difference is that:
in S1, the mass ratio of ferric nitrate, lithium hydroxide, ammonium fluoride, oxalic acid and deionized water is 100: 90: 30: 20: 500, a step of;
in S2, the calcination is to presintered for 8h at 300 ℃, and then the temperature is continuously raised to 700 ℃ for sintering for 15 h; nano-scale cobaltosic oxide and F-doped Li5FeO4The mass ratio of (A) to (B) is 5: 100, respectively;
in S3, the prelithiation additive and the positive electrode material LiNi0.8Co0.1Mn0.1O2The conductive agent carbon black and the binder PVDF are mixed according to the mass ratio of 8: 90: 1: 1, mixing to prepare slurry; controlling the compacted density to be 3.0g/cm3。
The rest is the same as in example 1.
Example 5
In S2, Co element in nano cobaltosic oxide and lithium sourceThe molar ratio of Li element is 1: 1.2; nano-scale cobaltosic oxide and F-doped Li5FeO4The mass ratio of (1): 1000, parts by weight;
in S3, the prelithiation additive and the positive electrode material LiNi0.8Co0.1Mn0.1O2The conductive agent carbon black and the binder PVDF are mixed according to the mass ratio of 5: 93: 1: 1, mixing to prepare slurry; controlling the compacted density to be 3.2g/cm3。
The rest is the same as in example 1.
Comparative example 1
The positive electrode material LiNi0.8Co0.1Mn0.1O2The conductive agent carbon black and the binder PVDF are mixed according to the mass ratio of 93: 6: 1, preparing slurry by mixing, controlling the solid content of the slurry to be 66%, then coating the slurry on an aluminum foil current collector, drying, rolling, and drying in vacuum at 80 ℃ for 12 hours to obtain the lithium ion battery positive pole piece, wherein the compaction density is controlled to be 3.2g/cm3。
Comparative example 2
S1, mixing ferric nitrate, lithium hydroxide, ammonium fluoride, oxalic acid and deionized water according to a mass ratio of 80: 70: 10: 7: 250, stirring and reacting to obtain sol, continuously stirring for 3h, heating and drying at 60 ℃ for 12h, grinding to obtain dry precursor powder, then raising the temperature from room temperature to 500 ℃ at the speed of 2 ℃/min for presintering for 5h, and cooling along with the furnace to obtain F-doped Li5FeO4；
S2, F-doped Li5FeO4Calcining, preburning at 500 ℃ for 5h, continuously raising the temperature to 800 ℃ for sintering for 12h, and cooling along with the furnace to obtain a prelithiation additive;
s3, pre-lithiation additive and positive electrode material LiNi0.8Co0.1Mn0.1O2The conductive agent carbon black and the binder PVDF are mixed according to the mass ratio of 5: 93: 1: 1, preparing slurry by mixing, controlling the solid content of the slurry to be 66%, then coating the slurry on an aluminum foil current collector, drying, rolling, and drying in vacuum at 80 ℃ for 12 hours to obtain the lithium ion battery positive pole piece, wherein the compaction density is controlled to be 3.2g/cm3。
The positive electrode sheets prepared in examples 1 to 5 and comparative examples 1 to 2 were used as a positive electrode, a negative electrode was graphite, and an electrolyte was 1mol/L LiPF6 (solute)/EC + DEC + EMC (solvent), respectively, and a monolithic pouch cell was assembled at an N/P ratio of 1.15, and electrochemical properties thereof were tested. Wherein, the first charge and discharge capacity, the first coulombic efficiency, the rate and the cycle data of example 1 and comparative examples 1-2 are shown in table 1, wherein the rate curves (0.2C, 0.33C, 1C, 0.2C return test, 1C) and the 50-week cycle curve at 1C are shown in fig. 1-2.
TABLE 1 electrochemical Performance data for example 1 and comparative examples 1-2
| Item | Example 1 | Comparative example 1 | Comparative example 2 |
| 0.2C first charger (mAh/g) | 235.4 | 229.0 | 230.4 |
| 0.2C head (mAh/g) | 208.1 | 198.8 | 201.5 |
| First coulombic efficiency (%) | 88.4 | 86.8 | 87.5 |
| 0.33C amplifier (mAh/g) | 204.4 | 196.1 | 198.3 |
| 1C amplifier (mAh/g) | 196.4 | 188.5 | 190.5 |
| 0.2C Return test (mAh/g) | 209.3 | 199.6 | 203.1 |
| |
196.3 | 188.5 | 191.9 |
| Circulation for 50 |
191.8 | 180.4 | 186.2 |
| 50-week capacity retention (%) | 97.7 | 95.7 | 97.0 |
As can be seen from table 1 and fig. 1 to 2, both the electrochemical performance and the capacity retention rate in example 1 are superior to those of comparative examples 1 and 2.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. The prelithiation additive for the anode material of the lithium ion battery is characterized in that the surface of the prelithiation additive is coated with LiCoO2F doped with Li5FeO4。
2. A preparation method of a prelithiation additive of a lithium ion battery positive electrode material is characterized by comprising the following steps:
s1, mixing an iron source, a lithium source, a fluorine source, a complexing agent and deionized water, stirring for reaction to obtain sol, continuing stirring for reaction, drying and grinding to obtain precursor powder, presintering and cooling to obtain F-doped Li5FeO4；
S2, F-doped Li5FeO4And nano-scale Co3O4Mixing with lithium source, calcining to obtain surface-coated LiCoO2F doped with Li5FeO4The prelithiation additive of (a).
3. The method for preparing the prelithiation additive of the lithium ion battery anode material according to claim 2, wherein in S1, the sol obtained is continuously stirred and reacted for 3h, heated and dried at 60 ℃ for 12h, and ground to obtain precursor powder; preferably, the pre-sintering is performed at 300-600 ℃ for 5-8 h.
4. The method for preparing the prelithiation additive for the positive electrode material of the lithium ion battery according to claim 2 or 3, wherein the iron source is one or more of ferric nitrate, ferric sulfate and ferric chloride; the lithium source is one or more of lithium hydroxide, lithium carbonate or lithium acetate; the fluorine source is ammonium fluoride; the complexing agent is oxalic acid.
5. The method for preparing the prelithiation additive of the lithium ion battery positive electrode material according to any one of claims 2 to 4, wherein in S1, the mass ratio of the iron source, the lithium source, the fluorine source, the complexing agent and the deionized water is 50 to 200: 25-300: 10-100: 5-100: 250 to 1000 parts; wherein the molar ratio of Fe element in the iron source to Li element in the lithium source is 1: 5 to 8.
6. The method for preparing the prelithiation additive for the positive electrode material of lithium ion battery according to any of claims 2 to 5, wherein in S2, nano-scale Co is added3O4The molar ratio of the medium Co element to the Li element in the lithium source is 1: 1 to 1.2; preferably, nanoscale Co3O4Li doped with F5FeO4The mass ratio of (A) to (B) is 1-50: 1000, parts by weight; preferably, nanoscale Co3O4Has a particle diameter of 50 to 500 nm.
7. The method for preparing the prelithiation additive of the lithium ion battery positive electrode material according to any one of claims 2 to 6, wherein in S2, the calcination is performed by pre-sintering at 300 to 500 ℃ for 3 to 8 hours, then heating to 700 to 900 ℃ for 8 to 15 hours, and the heating rate is 2 ℃/min.
8. The application of the prelithiation additive of the lithium ion battery positive electrode material prepared by the method of claim 1 or any one of claims 2 to 7 is characterized in that the prelithiation additive, the positive electrode material, the conductive agent and the binder are mixed to prepare slurry, the slurry is coated on a current collector, and the slurry is dried, rolled and dried to prepare the prelithiation lithium ion battery positive electrode piece.
9. The use of the prelithiation additive for the positive electrode material of a lithium ion battery according to claim 8, wherein in S3, the positive electrode material is a lithium nickel cobalt manganese ternary positive electrode material LiNixCoyMn1-x-yO2(x is more than or equal to 0 and less than or equal to 1); the conductive agent is one or more of carbon black, acetylene black, carbon nano tubes and graphene; the binder is PVDF.
10. The prelithiation method of the positive electrode material of the lithium ion battery according to claim 8, wherein the mass ratio of the prelithiation additive, the positive electrode material, the conductive agent and the binder is 0.5-10: 70-97.5: 1-10: 1-10% and the solid content of the slurry is 50-70%.
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