CN118598206A - Lithium supplementing agent and preparation method and application thereof - Google Patents
Lithium supplementing agent and preparation method and application thereof Download PDFInfo
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- CN118598206A CN118598206A CN202410767457.9A CN202410767457A CN118598206A CN 118598206 A CN118598206 A CN 118598206A CN 202410767457 A CN202410767457 A CN 202410767457A CN 118598206 A CN118598206 A CN 118598206A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 181
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 119
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000005245 sintering Methods 0.000 claims abstract description 88
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 56
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 28
- 239000010941 cobalt Substances 0.000 claims abstract description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims abstract description 21
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 56
- 229910052799 carbon Inorganic materials 0.000 claims description 43
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 28
- 239000011247 coating layer Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 18
- 239000011267 electrode slurry Substances 0.000 claims description 14
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 11
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 11
- 230000000630 rising effect Effects 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 239000013589 supplement Substances 0.000 claims description 8
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 16
- 239000013078 crystal Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 abstract description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 5
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 5
- 238000007142 ring opening reaction Methods 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 230000004992 fission Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 208000028659 discharge Diseases 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000010405 anode material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- -1 alkyl lithium Chemical compound 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910008722 Li2NiO2 Inorganic materials 0.000 description 1
- 229910001323 Li2O2 Inorganic materials 0.000 description 1
- 229910010699 Li5FeO4 Inorganic materials 0.000 description 1
- 229910010648 Li6CoO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000000654 additive Substances 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
- 239000006183 anode active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
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Classifications
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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 lithium supplementing agent, a preparation method and application thereof, and belongs to the technical field of lithium supplementing agents. The preparation of the lithium supplementing agent comprises the following steps: the mixture comprising the first lithium source and the cobalt source is subjected to a first sintering, and then mixed with the second lithium source and the nickel source and then subjected to a second sintering. The method can fully fuse and sinter the primary crystal grains of the lithium cobalt oxide by utilizing the surface energy provided by the first lithium source during the first sintering, thereby reducing the crystal grain size of the lithium cobalt oxide and reducing the corrosion of electrolyte caused by subsequent crystal lattice fission of the material. The lithium nickelate material generated by the second sintering can have part of Ni 3+ and/or Ni 4+ ions in a reaction system, and the nickel ions react with part of O 2‑ ions generated by lithium cobaltate under the electrochemical action to generate substances such as NiO and/or NiO 2, so that the ring-opening reaction of ethylene carbonate in the electrolyte is reduced when the O 2‑ ions react with the electrolyte, and the gas production is further reduced.
Description
Technical Field
The invention relates to the technical field of lithium supplementing agents, in particular to a lithium supplementing agent, a preparation method and application thereof.
Background
Energy is one of substances indispensable for the development of human society, and along with the development of society, the development of novel clean energy becomes a hot topic. In the development of new energy sources, lithium ion batteries are increasingly popular in the aspect of automobile power and energy storage due to the characteristics of high energy efficiency, long cycle life, low maintenance cost, flexible power and energy characteristics and the like.
However, with popularization of automobile electric drive, a lithium ion battery with higher energy density is a new target, since the first generation of lithium ion batteries are coming out, through updating of a chemical material system and optimization of internal and external structure design of the battery, the maximum energy density of the current commercial lithium ion battery can reach 300Wh/kg, and under the current design concept and material system, the difficulty of further improving the energy density is high, and the improvement is usually at the cost of safety, power and service life of the battery, the output input is low, and the cost is high. Another approach to increasing the energy density of a battery is to increase the energy of the battery by reducing the first loss of positive and negative electrode materials, i.e., by increasing the number of active lithium ions (as shown in fig. 1), primarily by adding positive or negative electrode additives, commonly referred to as lithium supplements. The cathode lithium supplementing agent has higher requirements on environment and process because of the need of introducing metal lithium or alkyl lithium, and has higher realization difficulty, while the anode lithium supplementing agent only needs to be mixed with a small amount of lithium supplementing agent (1-3 wt%) in the anode active material, does not change any front-section and middle-section process equipment, has simple operation and easy realization, and becomes the first choice of a plurality of battery enterprises.
The commonly adopted positive electrode lithium supplementing agent is that lithium-rich metal oxide, such as Li 6CoO4、Li5FeO4、Li2NiO2、Li2O2 and other materials, are added in the preparation process of a pole piece of a positive electrode material so as to compensate the efficiency loss of the first charge and discharge of the negative electrode. Taking Li 6CoO4 as an example, the action mechanism is as follows: in the primary charging process, the lithium supplementing agent can release specific capacity of more than 800mAh/g, and the primary discharge capacity is generally 30 mAh/g-40 mAh/g, and redundant lithium ions are generated to supplement the primary lithium loss of the graphite cathode and release oxygen.
The first charge and discharge mechanism of Li 6CoO4 is as follows:
Li6CoO4→Li6-xCoO4+xLi++xe-(x≤2)；
Li6-xCoO4→Li6-x-yCoOm+yLi++ye-+(2-m/2)O2(2-n)-(x＞2).
The charge-discharge curve of Li 6CoO4 is shown in fig. 2, and the XRD pattern of Li 6CoO4 at different charge states is shown in fig. 3.
Although the first charge capacity of Li 6CoO4 is above 800mAh/g, the first charge stage is about 3.3V, the second charge stage is about 3.7V, and compared with the charge stage of Li 5FeO4, the first charge capacity is about 0.2V lower, and the formation voltage can be effectively reduced in the formation stage. However, li 6CoO4 releases more O 2 during the first charging process, and the Co compound may react with the electrolyte more easily, catalyze the decomposition of the electrolyte, store gas, and affect the cycle performance of the battery.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a lithium supplementing agent, a preparation method and application thereof, so as to solve or improve the technical problems.
The invention can be realized as follows:
In a first aspect, the present invention provides a method for preparing a lithium-supplementing agent, comprising the steps of: sintering the mixture comprising the first lithium source and the cobalt source for the first time to obtain a lithium cobalt oxide material; mixing the lithium cobaltate material with a second lithium source and a nickel source, and then performing secondary sintering.
In an alternative embodiment, the mix comprises at least one of the following features:
characteristic one: the molar ratio of Li in the first lithium source to Co in the cobalt source is from 1.01:1 to 1.50:1;
And the second characteristic is: the first lithium source comprises at least one of lithium hydroxide, lithium oxide, lithium carbonate, and lithium acetate; preferably, the first lithium source comprises lithium hydroxide;
And (3) the following characteristics: d 50 of the first lithium source is 10-30 μm;
And four characteristics: the cobalt source includes at least one of CoO, co 3O4、CoCl2, and Co (OH) 2; preferably, the cobalt source comprises CoO;
and fifth feature: the mixture also comprises a carbon source; preferably, the carbon source comprises an organic carbon source; more preferably, the carbon source comprises at least one of glucose and acetylene; preferably, the addition amount of the carbon source is 0.1% -10% of the total mass of the Co source.
In an alternative embodiment, the first sintering includes at least one of the following features:
feature 1: the temperature of the first sintering is 600-900 ℃;
feature 2: the time of the first sintering is 8-15 h;
feature 3: the first sintering is carried out in inert atmosphere; preferably, the inert atmosphere comprises at least one of a nitrogen atmosphere and an argon atmosphere;
Feature 4: the temperature rising rate of the first sintering is 1-10 ℃/min.
In an alternative embodiment, the lithium cobaltate material is crushed a first time to obtain a first crushed material; mixing the first crushed material with a second lithium source and a nickel source, and then performing secondary sintering.
In an alternative embodiment, the first crushed material has a particle size in the range of 0.5 μm to 10 μm.
In an alternative embodiment, the molar ratio of Li in the second lithium source to Ni in the nickel source is from 1.05:1 to 1.3:1 and the molar ratio of Ni in the nickel source to Co in the first crushed material is from 0.1:1 to 10:1.
In an alternative embodiment, the second lithium source comprises at least one of lithium hydroxide, lithium oxide, lithium carbonate, and lithium acetate;
And/or the nickel source comprises at least one of Ni (OH) 2, niO, and NiCO 3.
In an alternative embodiment, the second lithium source comprises lithium oxide.
In an alternative embodiment, the second sintering includes at least one of the following features:
feature 5: the temperature of the second sintering is 500-800 ℃;
feature 6: the second sintering time is 5-15 h;
feature 7: sintering for the second time in inert atmosphere; preferably, the inert atmosphere comprises at least one of a nitrogen atmosphere and an argon atmosphere;
Feature 8: the temperature rising rate of the second sintering is 1-10 ℃/min.
In an alternative embodiment, the second sinter from the second sintering is subjected to a second crushing.
In an alternative embodiment, the particle size of the material after the second crushing is in the range of 3 μm to 15 μm.
In a second aspect, the present invention provides a lithium-supplementing agent prepared by the preparation method according to any one of the preceding embodiments.
In an alternative embodiment, the lithium supplement includes a lithium cobalt oxide material and a lithium nickel oxide material in contact with the lithium cobalt oxide material.
In an alternative embodiment, at least a portion of the lithium nickelate material coats the surface of the lithium cobaltate material.
In an alternative embodiment, the lithium supplement includes a lithium nickelate material and a lithium cobaltate material having a carbon coating layer; wherein, at least part of the lithium nickelate material forms a lithium nickelate coating layer on the surface of the carbon coating layer.
In an alternative embodiment, the carbon coating layer has a thickness of 10nm to 500nm.
In an alternative embodiment, the lithium nickelate coating layer has a thickness of 0.1 μm to 5 μm.
In a third aspect, the present invention provides a use of a lithium-supplementing agent according to the previous embodiments in the preparation of a battery.
In an alternative embodiment, the lithium-compensating agent is used in the preparation of a positive electrode sheet in a battery.
In an alternative embodiment, a lithium supplementing agent is used to prepare the positive electrode slurry of the positive electrode sheet.
In an alternative embodiment, the positive electrode slurry includes a lithium iron phosphate positive electrode material, a conductive agent, a binder, and a lithium supplementing agent.
In an alternative embodiment, the positive electrode slurry includes 0.5wt% to 5wt% of a lithium-supplementing agent, 92wt% to 98wt% of a lithium iron phosphate positive electrode material, 0.5wt% to 3wt% of a conductive agent, and the balance being a binder.
In an alternative embodiment, the negative electrode material of the battery is a graphite system material.
The beneficial effects of the invention include:
According to the preparation method of the lithium supplementing agent, in the first sintering process, the surface energy provided by the first lithium source in the molten state can fully fuse and sinter primary crystal grains of lithium cobalt oxide, so that the crystal grain size of the lithium cobalt oxide can be reduced, and the corrosion of electrolyte caused by subsequent crystal lattice fission of a material is reduced. The lithium nickelate material generated by the second sintering can have part of Ni 3+ and/or Ni 4+ ions in a reaction system, and the nickel ions react with part of O 2- ions generated by lithium cobaltate under the electrochemical action to generate substances such as NiO and/or NiO 2, so that the ring-opening reaction of ethylene carbonate in the electrolyte is reduced when the O 2- ions react with the electrolyte, and the gas production is further reduced. The lithium supplementing agent is applied to a battery with a lithium iron phosphate anode material and a graphite system cathode material, can improve the charge-discharge specific capacity and the cycle retention rate of the battery, and can reduce the gas production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram showing the relationship between the number of active lithium ions and the battery energy of a lithium battery in the background art;
FIG. 2 is a graph of the charge and discharge of Li 6CoO4 in the background;
FIG. 3 is an XRD pattern of Li 6CoO4 in different states of charge in the background;
Fig. 4 is a schematic structural diagram of a lithium-supplementing agent according to embodiment 1 of the present invention;
Fig. 5 is a graph showing the comparison result of the dc resistances of the batteries obtained in accordance with example 1 and comparative example 2 in the test example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The lithium supplementing agent, the preparation method and the application thereof provided by the application are specifically described below.
The application provides a preparation method of a lithium supplementing agent, which comprises the following steps: sintering the mixture comprising the first lithium source and the cobalt source for the first time to obtain a lithium cobalt oxide material; mixing the lithium cobaltate material with a second lithium source and a nickel source, and then performing secondary sintering.
In the first sintering process, the surface energy provided by the first lithium source in a molten state can fully fuse and sinter primary crystal grains of lithium cobalt oxide, so that the crystal grain size of the lithium cobalt oxide can be reduced, and the corrosion of electrolyte caused by subsequent crystal lattice fission of the material is reduced. The lithium nickelate material generated by the second sintering can have part of Ni 3+ and/or Ni 4+ ions in a reaction system, and the nickel ions react with part of O 2- ions generated by lithium cobaltate under the electrochemical action to generate substances such as NiO and/or NiO 2, so that the ring-opening reaction of ethylene carbonate in the electrolyte is reduced when the O 2- ions react with the electrolyte, and the gas production is further reduced.
In the alternative, the molar ratio of Li in the first lithium source to Co in the cobalt source may be 1.01:1 to 1.50:1, such as 1.01:1, 1.05:1, 1.10:1, 1.15:1, 1.20:1, 1.25:1, 1.30:1, 1.35:1, 1.40:1, 1.45:1, or 1.50:1, etc., as well as other values in the range of 1.01:1 to 1.50:1.
If the molar ratio of Li in the first lithium source to Co in the cobalt source is less than 1.01:1 (e.g., 1:1), it is unfavorable to form a stable Li 6CoO4 structure; if the molar ratio of Li in the first lithium source to Co in the cobalt source is greater than 1.50:1 (e.g., 1.60:1), this tends to result in waste of the Li source, and excessive Li formation and reaction of H 2 O and CO 2 in the air to form impurities.
The first lithium source may include, by way of example and not limitation, at least one of lithium hydroxide, lithium oxide, lithium carbonate, and lithium acetate. In some more typical embodiments, the first lithium source comprises lithium hydroxide.
In the alternative, D 50 of the first lithium source may be 10 μm to 30 μm, such as 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm, etc., or any other value in the range of 10 μm to 30 μm.
If D 50 of the first lithium source is less than 10 μm, the reaction with Co is not facilitated; if D 50 of the first lithium source is larger than 30 μm, uniform mixing is not favored.
The cobalt source may include, by way of example and not limitation, at least one of CoO, co 3O4、CoCl2, and Co (OH) 2. In some more typical embodiments, the cobalt source comprises CoO.
In some alternatives, a carbon source may also be included in the mix. The carbon source may include an organic carbon source, such as may include at least one of glucose and acetylene. The carbon source may be added in an amount of 0.1% to 10% by mass, such as 0.1%, 0.5%, 1%, 2%, 4%, 6%, 8% or 10% by mass, of the total mass of the Co source, or may be added in an amount of other values within the range of 0.1% to 10%.
In some alternatives, the mixture may be mixed from the first lithium source, the cobalt source, and the carbon source in a ball mill. The rotational speed during mixing may be, for example, 1000rpm to 10000rpm, such as 1000rpm, 2000rpm, 5000rpm, 8000rpm or 10000rpm, or other values in the range of 1000rpm to 10000 rpm.
In the alternative, the temperature of the first sintering may be 600 ℃ to 900 ℃, such as 600 ℃, 650 ℃,700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, or the like, but may also be other values in the range of 600 ℃ to 900 ℃.
The time of the first sintering may be 8h to 15h, such as 8h, 9h, 10h, 11h, 12h, 13h, 14h or 15h, etc., and may be other values in the range of 8h to 15 h.
If the temperature of the first sintering is less than 600 ℃ or the time of the first sintering is shorter than 8 hours, the stable Li 6CoO4 structure is not formed; if the temperature of the first sintering is higher than 900 ℃ or the time of the first sintering is longer than 15 hours, the material structure is easy to collapse, the crystal structure is damaged, and the capacity is influenced.
The heating rate of the first sintering may be 1 to 10 ℃ per minute, such as 1 to 2 ℃ per minute, 3 ℃ per minute, 4 ℃ per minute, 5 ℃ per minute, 6 ℃ per minute, 7 ℃ per minute, 8 ℃ per minute, 9 ℃ per minute or 10 ℃ per minute, or other values within the range of 1 to 10 ℃ per minute.
The first sintering is performed in an inert atmosphere. The inert atmosphere may include, by way of example and not limitation, at least one of a nitrogen atmosphere and an argon atmosphere.
The lithium cobalt oxide material can be produced by performing the first sintering of the mixture under the above conditions, and when the mixture contains a carbon source, the surface of the lithium cobalt oxide material has a carbon coating layer, which is beneficial to improving the conductivity of the lithium cobalt oxide material.
Further, the material obtained by the first sintering can be crushed for the first time to obtain a first crushed material; mixing the first crushed material with a second lithium source and a nickel source, and then performing secondary sintering.
In some alternatives, the mixing of the first crushed material with the second lithium source and the nickel source may be performed in a high speed mixer, the rotational speed during the mixing may be, for example, 1000rpm to 10000rpm, such as 1000rpm, 2000rpm, 5000rpm, 8000rpm or 10000rpm, etc., but may also be other values in the range of 1000rpm to 10000 rpm.
Illustratively, the particle size of the first crushed material may range from 0.5 μm to 10 μm, such as 0.5 μm,1 μm,2 μm, 4 μm, 6 μm, 8 μm or 10 μm, etc., and may be other values in the range from 0.5 μm to 10 μm.
In some alternatives, the molar ratio of Li in the second lithium source to Ni in the nickel source may be 1.05:1 to 1.3:1, such as 1.05:1, 1.1:1, 1.15:1, 1.2:1, 1.25:1, or 1.3:1, etc., as well as other values in the range of 1.05:1 to 1.3:1. The molar ratio of Ni in the nickel source to Co in the first crushed material may be 0.1:1 to 10:1, such as 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1, etc., and may be other values in the range of 0.1:1 to 10:1.
The second lithium source may include, by way of example and not limitation, at least one of lithium hydroxide, lithium oxide, lithium carbonate, and lithium acetate. In some more typical embodiments, the second lithium source comprises lithium oxide.
The nickel source may include, by way of example and not limitation, at least one of Ni (OH) 2, niO, and NiCO 3.
In the alternative, the temperature of the second sintering may be 500 ℃ to 800 ℃, such as 500 ℃, 550 ℃, 600 ℃, 650 ℃,700 ℃, 750 ℃, 800 ℃, or the like, but may also be other values in the range of 500 ℃ to 800 ℃.
The second sintering time may be 5h to 15h, such as 5h, 8h, 10h, 12h or 15h, or may be other values within the range of 5h to 15 h.
The temperature rising rate of the second sintering can be 1-10 ℃ per minute, such as 1-10 ℃ per minute, 2 ℃ per minute, 3 ℃ per minute, 4 ℃ per minute, 5 ℃ per minute, 6 ℃ per minute, 7 ℃ per minute, 8 ℃ per minute, 9 ℃ per minute or 10 ℃ per minute, and the like, and can also be other values within the range of 1-10 ℃ per minute. In some preferred embodiments, the first sintering corresponds to a higher rate of temperature rise than the second sintering.
The second sintering is also performed in an inert atmosphere. Similarly, the inert atmosphere for the second sintering may include, by way of example and not limitation, at least one of a nitrogen atmosphere and an argon atmosphere.
Further, the second sintered material obtained by the second sintering may be subjected to the second crushing.
Illustratively, the particle size of the material after the second crushing may be in the range of 3 μm to 15 μm, such as 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, etc., and may be other values in the range of 3 μm to 15 μm.
And the materials after the second crushing can be screened according to the requirement.
Correspondingly, the invention provides a lithium supplementing agent which is prepared by the preparation method.
The lithium supplement includes a lithium cobalt oxide material and a lithium nickel oxide material in contact with the lithium cobalt oxide material.
When the surface of the lithium cobaltate material is not provided with the carbon coating layer, at least part of the lithium nickelate material is directly coated on the surface of the lithium cobaltate material to form the lithium nickelate coating layer. When the surface of the lithium cobaltate material is provided with a carbon coating layer, the lithium supplementing agent comprises a lithium nickelate material and a lithium cobaltate material with a carbon coating layer; at least a portion of the lithium nickelate material forms a lithium nickelate coating on the surface of the carbon coating.
It should be noted that the number of the components, the lithium nickelate coating layer may be continuous or discontinuous. When the lithium nickelate coating layer is continuous, it may have only a coating structure formed by the lithium nickelate material continuously; in addition, the continuous coating structure formed by partial lithium nickel oxide material can also independently contain partial lithium nickel oxide material in particle form. When the lithium nickelate coating is discontinuous, the lithium nickelate material coats the lithium nickelate material or the carbon coating in particulate form, i.e. with gaps between at least part of the lithium nickelate particles.
The lithium nickelate material has part of Ni 3+ and/or Ni 4+ ions in a reaction system, and the nickel ions can react with part of O 2- ions generated by lithium cobaltate under the electrochemical action to generate substances such as NiO and/or NiO 2, so that the ring-opening reaction of ethylene carbonate in the electrolyte is reduced when the O 2- ions react with the electrolyte, and the gas production is further reduced.
For reference, the thickness of the carbon coating layer may be 10nm to 500nm (e.g., 10nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, etc.). The thickness of the lithium nickelate coating layer may be 0.1 μm to 5 μm (e.g., 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, etc.).
The lithium supplementing agent has higher specific capacity and cycle retention rate, and less gas production.
In addition, the invention also provides application of the lithium supplementing agent in battery preparation.
In some alternative approaches, lithium-compensating agents are used in the preparation of positive electrode sheets in batteries. Illustratively, the battery may be a lithium iron phosphate (abbreviated as "LFP") battery, and the negative electrode material in the negative electrode may be a graphite system material.
Specifically, the lithium supplementing agent can be used for preparing positive electrode slurry of a positive electrode plate. The positive electrode slurry may include a lithium iron phosphate positive electrode material, a conductive agent, a binder, and a lithium supplementing agent.
Wherein the positive electrode slurry may include 0.5wt% to 5wt% (e.g., 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, or 5wt%, etc.) of a lithium supplementing agent, 92wt% to 98wt% (e.g., 92wt%, 93wt%, 94wt%, 95wt%, 96wt%, 97wt%, or 98wt%, etc.) of a lithium iron phosphate positive electrode material, 0.5wt% to 3wt% (e.g., 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, or 3wt%, etc.), and the balance being a binder.
Illustratively, the binder may include at least one of polyvinylidene fluoride, styrene-butadiene rubber, and polyvinyl alcohol. The conductive agent may include at least one of carbon nanotubes, super-P, and graphene.
The preparation conditions and methods of the other related batteries can be referred to the related prior art, and are not described in detail herein.
The lithium supplementing agent provided by the invention is used for a battery with a lithium iron phosphate anode material and a graphite system cathode material, so that the direct current internal resistance of the battery can be effectively reduced, and the electrochemical performance of the battery can be improved.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a lithium supplementing agent, and the preparation method comprises the following steps:
s1: and (5) preparing a mixture.
And mixing the first lithium source, the cobalt source and the carbon source in a ball mill to obtain a mixture. Wherein the first lithium source is LiOH with D 50 of 20 μm, the cobalt source is CoO, and the carbon source is glucose. The molar ratio of Li in the first lithium source to Co in the cobalt source was 1.05:1, and the carbon source was added in an amount of 2.5wt% of the mixture. The mixing speed was 5000rpm and the mixing time was 10 hours.
S2: and (5) sintering for the first time.
And (3) performing primary sintering on the mixture obtained in the step (S1) in an argon atmosphere. The temperature of the first sintering is 700 ℃, the time of the first sintering is 10 hours, and the temperature rising speed is 5 ℃/min, so that the lithium cobalt oxide material is obtained; the lithium cobaltate material is crushed for the first time to obtain a first crushed material with the particle size ranging from 0.5 mu m to 10 mu m.
S3: and (5) mixing materials for the second time.
The second lithium source, the nickel source, and the first crushed material obtained by S2 are mixed in a high-speed mixer. Wherein the second lithium source is lithium oxide, the nickel source is Ni (OH) 2, the molar ratio of Li in the second lithium source to Ni in the nickel source is 1.05:1, and the molar ratio of Ni in the nickel source to Co in the first crushed material is 2:1. The mixing speed was 3000rpm and the mixing time was 10 hours.
S4: and sintering for the second time.
And (3) sintering the mixed material obtained in the step (S3) for the second time in an argon atmosphere. The temperature of the second sintering is 800 ℃, the time of the second sintering is 8 hours, and the temperature rising speed is 2 ℃/min, so as to obtain the second sintering material. And crushing the second sintered material for the second time to obtain a second crushed material with the particle size ranging from 3 mu m to 15 mu m, and screening the second crushed material to obtain the lithium supplementing agent with the average particle size of 10 mu m.
Example 2
This embodiment differs from embodiment 1 in that: the temperature of the first sintering was 600 ℃.
Example 3
This embodiment differs from embodiment 1 in that: the temperature of the first sintering was 800 ℃.
Example 4
This embodiment differs from embodiment 1 in that: the molar ratio of Li in the first lithium source to Co in the cobalt source was 1.02:1.
Example 5
This embodiment differs from embodiment 1 in that: the molar ratio of Li in the first lithium source to Co in the cobalt source was 1.1:1.
Example 6
This embodiment differs from embodiment 1 in that: the molar ratio of Li in the first lithium source to Co in the cobalt source was 1.15:1.
Example 7
This embodiment differs from embodiment 1 in that: the molar ratio of Ni in the nickel source to Co in the first crushed material was 3:1.
Example 8
This embodiment differs from embodiment 1 in that: the molar ratio of Ni in the nickel source to Co in the first crushed material was 4:1.
Example 9
This embodiment differs from embodiment 1 in that: the mixture of S1 contains no carbon source.
Example 10
The embodiment provides a lithium supplementing agent, and the preparation method comprises the following steps:
s1: and (5) preparing a mixture.
And mixing the first lithium source, the cobalt source and the carbon source in a ball mill to obtain a mixture. Wherein the first lithium source is lithium oxide with D 50 of 10 mu m, the cobalt source is Co 3O4, and the carbon source is acetylene. The molar ratio of Li in the first lithium source to Co in the cobalt source was 1.01:1, and the carbon source was added in an amount of 2.5wt% of the mixture. The mixing speed was 5000rpm and the mixing time was 10 hours.
S2: and (5) sintering for the first time.
And (3) performing primary sintering on the mixture obtained in the step (S1) in a nitrogen atmosphere. The temperature of the first sintering is 600 ℃, the time of the first sintering is 10 hours, and the temperature rising speed is 1 ℃/min, so that the lithium cobalt oxide material is obtained; the lithium cobaltate material is crushed for the first time to obtain a first crushed material with the particle size ranging from 0.5 mu m to 10 mu m.
S3: and (5) mixing materials for the second time.
The second lithium source, the nickel source, and the first crushed material obtained by S2 are mixed in a high-speed mixer. The second lithium source is lithium hydroxide, the nickel source is NiO, the molar ratio of Li in the second lithium source to Ni in the nickel source is 1.05:1, and the molar ratio of Ni in the nickel source to Co in the first crushed material is 0.1:1. The mixing speed was 3000rpm and the mixing time was 10 hours.
S4: and sintering for the second time.
And (3) carrying out secondary sintering on the mixed material obtained in the step (S3) in a nitrogen atmosphere. The temperature of the second sintering is 500 ℃, the time of the second sintering is 8 hours, and the temperature rising speed is 1 ℃/min, so as to obtain the second sintering material. And crushing the second sintered material for the second time to obtain a second crushed material with the particle size ranging from 3 mu m to 15 mu m, and screening the second crushed material to obtain the lithium supplementing agent with the average particle size of 10 mu m.
Example 11
The embodiment provides a lithium supplementing agent, and the preparation method comprises the following steps:
s1: and (5) preparing a mixture.
And mixing the first lithium source, the cobalt source and the carbon source in a ball mill to obtain a mixture. Wherein the first lithium source is lithium carbonate with D 50 of 30 μm, the cobalt source is Co (OH) 2, and the carbon source is glucose. The molar ratio of Li in the first lithium source to Co in the cobalt source was 1.50:1, and the carbon source was added in an amount of 2.5wt% of the mixture. The mixing speed was 5000rpm and the mixing time was 10 hours.
S2: and (5) sintering for the first time.
And (3) performing primary sintering on the mixture obtained in the step (S1) in a nitrogen atmosphere. The temperature of the first sintering is 900 ℃, the time of the first sintering is 10 hours, and the temperature rising speed is1 ℃/min, so that the lithium cobalt oxide material is obtained; the lithium cobaltate material is crushed for the first time to obtain a first crushed material with the particle size ranging from 0.5 mu m to 10 mu m.
S3: and (5) mixing materials for the second time.
The second lithium source, the nickel source, and the first crushed material obtained by S2 are mixed in a high-speed mixer. Wherein the second lithium source is lithium carbonate, the nickel source is NiCO 3, the molar ratio of Li in the second lithium source to Ni in the nickel source is 1.3:1, and the molar ratio of Ni in the nickel source to Co in the first crushed material is 10:1. The mixing speed was 3000rpm and the mixing time was 10 hours.
S4: and sintering for the second time.
And (3) carrying out secondary sintering on the mixed material obtained in the step (S3) in a nitrogen atmosphere. The temperature of the second sintering is 700 ℃, the time of the second sintering is 8 hours, and the temperature rising speed is 8 ℃/min, so as to obtain the second sintering material. And crushing the second sintered material for the second time to obtain a second crushed material with the particle size ranging from 3 mu m to 15 mu m, and screening the second crushed material to obtain the lithium supplementing agent with the average particle size of 10 mu m.
Comparative example 1
The lithium supplement of this comparative example was the first crushed material of example 1, which did not use a carbon source in the preparation process.
Comparative example 2
The lithium supplement of this comparative example was the first crushed material in example 1.
Test examples
① . Taking the lithium supplementing agent prepared in example 1 as an example, as shown in fig. 4, the lithium supplementing agent comprises a lithium nickelate material and a lithium cobaltate material with a carbon coating layer, wherein part of the lithium nickelate material forms a continuous lithium nickelate coating layer on the surface of the carbon coating layer, and part of the lithium nickelate material exists in the lithium supplementing agent in a particle form. Wherein the thickness of the carbon coating layer is 10 nm-500 nm, and the thickness of the lithium nickelate coating layer is 0.1 mu m-5 mu m.
② . The lithium-supplementing agents prepared in examples 1 to 11 and comparative examples 1 to 2 were added to the positive electrode slurry and further prepared into batteries, respectively, in the following manner.
Preparation of positive electrode slurry: lithium iron phosphate positive electrode material, conductive agent (Super P), binder (PVDF) and lithium supplementing agent are mixed according to the ratio of 95:2:0.5:2.5.
The negative electrode adopts a graphite system, and the specific preparation method of the negative electrode slurry is as follows: graphite anode material, conductive agent (Super P), binder (PVDF), dispersant (CMC) were mixed according to 96.6:0.5:1.8:1.1.
And then respectively coating the positive electrode slurry and the negative electrode slurry on a positive electrode current collector (aluminum foil) and a negative electrode current collector (copper foil), and preparing the battery according to the steps of rolling, slitting, lamination, assembly, liquid injection, sealing and formation.
A. The batteries obtained in examples 1 to 11 and comparative examples 1 to 2 were subjected to specific charge tests under the following conditions: the constant current 0.1C was charged to 4.3V, the constant voltage was constant to 0.02C, and the constant current 0.1C was discharged to 2.0V, and the results are shown in table 1.
Table 1 test results
| Specific charge capacity/mAh/g | |
| Comparative example 1 | 712 |
| Comparative example 2 | 784 |
| Example 1 | 739 |
| Example 2 | 683 |
| Example 3 | 715 |
| Example 4 | 650 |
| Example 5 | 688 |
| Example 6 | 703 |
| Example 5 | 716 |
| Example 6 | 699 |
B. The batteries obtained were subjected to a full-cell discharge specific capacity, a capacity retention after 45 cycles, and a gas production condition using examples 1 and comparative example 2, and the results are shown in table 2.
The full-battery discharge specific capacity and the capacity retention rate after 45 circles of circulation are carried out according to the condition in A, and the gas production test method is that the volume is measured by a drainage method. "D" stands for "day".
Table 2 test results
| Specific discharge capacity/mAh/g of full battery | 45 Cycle capacity retention/% | Gas production | |
| Comparative example 2 | 147.45 | 89.67% 1000 Weeks | 35D@10.67％ |
| Example 1 | 146.98 | 1000 Weeks 93.63% | 35D@5.34％ |
As can be seen from tables 1 and 2, the lithium supplementing agent provided by the embodiment of the invention is applied to a battery with a positive electrode material of lithium iron phosphate and a negative electrode material of a graphite system, and can improve the charge-discharge specific capacity and the cycle retention rate of the battery and reduce the gas production.
C. the results of comparing the dc resistances of the obtained batteries are shown in fig. 5, taking example 1 and comparative example 2 as examples.
As can be seen from fig. 5: the lithium supplementing agent provided by the invention is used for a battery with a lithium iron phosphate anode material and a graphite system cathode material, and can effectively reduce the direct current internal resistance of the battery.
In summary, in the preparation method of the lithium supplementing agent provided by the invention, in the first sintering process, the surface energy provided by the first lithium source in the molten state can fully fuse and sinter the primary crystal grains of lithium cobalt oxide, so that the crystal grain size of lithium cobalt oxide can be reduced, and the corrosion of electrolyte caused by subsequent crystal lattice fission of the material is reduced. The lithium nickelate material generated by the second sintering can have part of Ni 3+ and/or Ni 4+ ions in a reaction system, and the nickel ions react with part of O 2- ions generated by lithium cobaltate under the electrochemical action to generate substances such as NiO and/or NiO 2, so that the ring-opening reaction of ethylene carbonate in the electrolyte is reduced when the O 2- ions react with the electrolyte, and the gas production is further reduced. The lithium supplementing agent is applied to a battery with a lithium iron phosphate anode material and a graphite system cathode material, can improve the charge-discharge specific capacity and the cycle retention rate of the battery, and can reduce the gas production.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the lithium supplementing agent is characterized by comprising the following steps of: sintering the mixture comprising the first lithium source and the cobalt source for the first time to obtain a lithium cobalt oxide material; and mixing the lithium cobaltate material with a second lithium source and a nickel source, and then performing secondary sintering.
2. The method of claim 1, wherein the blend comprises at least one of the following characteristics:
characteristic one: the molar ratio of Li in the first lithium source to Co in the cobalt source is from 1.01:1 to 1.50:1;
And the second characteristic is: the first lithium source comprises at least one of lithium hydroxide, lithium oxide, lithium carbonate, and lithium acetate; preferably, the first lithium source comprises lithium hydroxide;
And (3) the following characteristics: d 50 of the first lithium source is 10-30 mu m;
and four characteristics: the cobalt source includes at least one of CoO, co 3O4、CoCl2, and Co (OH) 2; preferably, the cobalt source comprises CoO;
And fifth feature: the mixture also comprises a carbon source; preferably, the carbon source comprises an organic carbon source; more preferably, the carbon source comprises at least one of glucose and acetylene; preferably, the addition amount of the carbon source is 0.1% -10% of the total mass of the Co source.
3. The method of manufacturing according to claim 1 or 2, characterized in that the first sintering comprises at least one of the following features:
feature 1: the temperature of the first sintering is 600-900 ℃;
feature 2: the time of the first sintering is 8-15 h;
Feature 3: the first sintering is carried out in inert atmosphere; preferably, the inert atmosphere comprises at least one of a nitrogen atmosphere and an argon atmosphere;
Feature 4: the temperature rising rate of the first sintering is 1-10 ℃/min.
4. A method of preparing according to claim 3, wherein the lithium cobaltate material is subjected to a first crushing to obtain a first crushed material; mixing the first crushed material with the second lithium source and the nickel source, and then performing secondary sintering;
Preferably, the first crushed material has a particle size ranging from 0.5 μm to 10 μm.
5. The method of claim 4, wherein the molar ratio of Li in the second lithium source to Ni in the nickel source is from 1.05:1 to 1.3:1 and the molar ratio of Ni in the nickel source to Co in the first crushed material is from 0.1:1 to 10:1.
6. The method of preparing according to claim 5, wherein the second lithium source comprises at least one of lithium hydroxide, lithium oxide, lithium carbonate, and lithium acetate;
And/or the nickel source comprises at least one of Ni (OH) 2, niO, and NiCO 3;
preferably, the second lithium source comprises lithium oxide.
7. The method of manufacturing according to claim 1, wherein the second sintering comprises at least one of the following features:
feature 5: the temperature of the second sintering is 500-800 ℃;
feature 6: the second sintering time is 5-15 h;
feature 7: sintering for the second time in inert atmosphere; preferably, the inert atmosphere comprises at least one of a nitrogen atmosphere and an argon atmosphere;
Feature 8: the temperature rising rate of the second sintering is 1-10 ℃/min.
8. The method according to claim 7, wherein the second sintered material obtained by the second sintering is subjected to the second crushing;
preferably, the particle size of the material after the second crushing is in the range of 3 μm to 15. Mu.m.
9. A lithium supplementing agent characterized by being prepared by the preparation method according to any one of claims 1 to 8;
preferably, the lithium supplement comprises a lithium cobaltate material and a lithium nickelate material in contact with the lithium cobaltate material;
preferably, at least part of the lithium nickelate material is coated on the surface of the lithium cobaltate material;
Preferably, the lithium supplementing agent comprises a lithium nickelate material and a lithium cobaltate material with a carbon coating layer; wherein, at least part of the lithium nickelate material forms a lithium nickelate coating layer on the surface of the carbon coating layer;
preferably, the thickness of the carbon coating layer is 10 nm-500 nm;
Preferably, the thickness of the lithium nickelate coating layer is 0.1 μm to 5 μm.
10. Use of the lithium-compensating agent of claim 9 in the preparation of a battery;
Preferably, the lithium supplementing agent is used for preparing a positive electrode plate in a battery;
Preferably, the lithium supplementing agent is used for preparing positive electrode slurry of the positive electrode plate;
Preferably, the positive electrode slurry comprises a lithium iron phosphate positive electrode material, a conductive agent, a binder and the lithium supplementing agent;
Preferably, the positive electrode slurry comprises 0.5 to 5wt% of the lithium supplementing agent, 92 to 98wt% of the lithium iron phosphate positive electrode material, 0.5 to 3wt% of the conductive agent, and the balance of the binder;
preferably, the negative electrode material of the battery is a graphite system material.
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