CN114684850B - Zinc-based pre-lithiated material and preparation method and application thereof - Google Patents
Zinc-based pre-lithiated material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 100
- 239000011701 zinc Substances 0.000 title claims abstract description 62
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 62
- 238000006138 lithiation reaction Methods 0.000 claims abstract description 19
- 239000011787 zinc oxide Substances 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 40
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000011265 semifinished product Substances 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 5
- 239000011667 zinc carbonate Substances 0.000 claims description 5
- 235000004416 zinc carbonate Nutrition 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000001502 supplementing effect Effects 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000000840 electrochemical analysis Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 230000009469 supplementation Effects 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- -1 nickel cobalt aluminum Chemical compound 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/625—Carbon or graphite
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- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape
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- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
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Abstract
The invention discloses a zinc-based pre-lithiation material, a preparation method and application thereof, wherein the structural general formula of the zinc-based pre-lithiation material is Li xZnOy, wherein 1<x is less than or equal to 6, and y is more than or equal to 2 and less than or equal to 4. The granularity of the zinc-based pre-lithiation material is between 50nm and 50um, the lithium removal capacity is between 200mAh/g and 1000mAh/g, and the lithium removal voltage is between 3 and 6V. The zinc-based pre-lithiation material can be added into a positive electrode plate, and releases capacity during the first formation, thereby playing a role in supplementing active lithium ions in a battery. The preparation method is simple, is compatible with the existing battery core preparation process, is easy to realize industrialization, and can improve the first-circle coulomb efficiency and the energy density of the lithium ion battery.
Description
[ Field of technology ]
The invention relates to the technical field of lithium battery materials, in particular to a zinc-based pre-lithiation material, a preparation method and application thereof.
[ Background Art ]
Lithium ion batteries have been widely used as an important energy storage device in the fields of consumer electronics, energy storage grids, electric automobiles and the like due to the advantages of high voltage, large capacity, high energy density and the like. At present, the most commonly used negative electrode of a lithium ion battery is graphite, and in the process of first charge and discharge of the lithium ion battery, an electrolyte solution is reduced and decomposed on the surface of the graphite to form a solid electrolyte film (SEI film), so that a large amount of active lithium from a positive electrode is permanently consumed, the first-time in-store efficiency is low, the reversible active lithium in the battery is reduced, and the capacity and the energy density of the battery are reduced. The existing graphite negative electrode has 5% -10% of loss of irreversible active lithium at the first week, and more loss of irreversible active lithium at the first week is caused for high-capacity negative electrodes such as hard carbon, silicon carbon negative electrodes and the like.
The pre-lithiation technology is a key method for solving the problem, and the electrode pole piece is subjected to lithium supplementation before circulation through pre-lithiation to offset irreversible loss caused by formation of an SEI film so as to improve the capacity and energy density of the battery. Common prelithiation technologies include lithium foil lithium supplementation and lithium powder lithium supplementation, such as patent CN201480026582 and CN201210056121, which have very severe environmental requirements, require very high dry environments to operate and process metallic lithium, are difficult to control, have higher requirements on the environment and equipment, and have certain operation safety hazards. Therefore, the lithium is supplemented to the positive electrode by using a material with Li more than 1.0, which is more compatible with the existing preparation process, and is a very promising pre-lithiation technology. However, the existing prelithiation technology has the defects of over high price and insufficient prelithiation capacity. Specifically, the lithium foil lithium powder is mainly prepared from metal lithium, the operation environment and equipment requirements are too high, the preparation difficulty of the lithium foil lithium powder is also high, and the cost is high; the lithium supplementing capacity of the anode is insufficient, mainly because the lithium supplementing material can provide limited active lithium and has low self capacity, the addition amount is usually lower than 10% when the lithium supplementing material is used, and the capacity of the whole system is improved by only a few mAh/g finally.
[ Invention ]
The invention discloses a zinc-based pre-lithiation material, a preparation method and application thereof, wherein the modified pre-lithiation material can greatly improve the capacity of a lithium battery, and the preparation method is simple, has low environmental requirements, is rich in raw materials and is suitable for large-scale production.
The invention aims at realizing the following technical scheme:
The structural general formula of the zinc-based pre-lithiation material is Li xZnOy, wherein 1<x is less than or equal to 6, and y is more than or equal to 2 and less than or equal to 4.
The granularity of the zinc-based pre-lithiation material is between 50nm and 50um, the lithium removal capacity is between 200mAh/g and 1000mAh/g, and the lithium removal voltage is between 3 and 6V.
Preferably, the particle size of the zinc-based prelithiation material is between 100nm and 1 um.
Preferably, the delithiation capacity of the zinc-based prelithiated material is between 300mAh/g and 950 mAh/g.
More preferably, the delithiation capacity of the zinc-based prelithiated material is between 400mAh/g and 950 mAh/g.
Preferably, the delithiation voltage of the zinc-based pre-lithiated material is between 3 and 4.6V.
Preferably, the particle shape of the zinc-based pre-lithiated material is one or more of circular, elliptical, sheet-like, and polygonal.
Preferably, the zinc-based pre-lithiated material can be used in combination with a carbon material, and the carbon material is uniformly or unevenly coated on the surface of the zinc-based pre-lithiated material. The carbon-coated zinc-based pre-lithium material follows the compounding, which is to increase the electrical conductivity of the material (and may also slightly increase the air stability of the material, depending on the thickness of the coated carbon), since pre-lithium materials generally have relatively poor kinetic properties, and the electrical conductivity can be significantly increased by carbon coating.
Preferably, the carbon material comprises one or more of amorphous carbon, graphene, carbon nanotubes, conductive graphite.
Preferably, the mass ratio of the carbon material to the zinc-based pre-lithiated material is between 1:1000 and 1:1.
More preferably, the mass ratio of the carbon material to the zinc-based pre-lithiated material is between 1:1000 and 1:20.
The invention also provides a preparation method of the zinc-based pre-lithiated material, which comprises the following steps: ball-milling and mixing a lithium source and a zinc source in a molar ratio of 2:1-6:1, sintering in sintering equipment, cooling to room temperature, and fully crushing the obtained material to obtain the zinc-based prelithiation material. It is usually necessary to carry out the pulverization twice, once or three times, and the pulverization is carried out until the particle size is 50nm to 50um as mentioned in claim 2, and the manner of the pulverization is usually twice.
Preferably, the lithium source is one or more of lithium carbonate, lithium hydroxide, and lithium acetate.
Preferably, the zinc source is one or more of zinc oxide, zinc carbonate and zinc acetate.
More preferably, the particle size of the lithium source and zinc source is between 10nm and 100 um.
Preferably, the ball milling and mixing device comprises one of a double-motion mixer, a three-dimensional mixer, a V-shaped mixer, a single cone double screw mixer, a groove type ribbon mixer and a horizontal gravity-free mixer.
Preferably, the sintering equipment comprises one of a box furnace, a tube furnace, a roller kiln and a rotary kiln.
Preferably, the crushing apparatus comprises one of a jaw crusher, a cone crusher, a counter-impact crusher, a hammer crusher and a roller crusher.
Preferably, the pulverizing apparatus includes one of a flat jet mill, a fluidized bed jet mill, a circulating jet mill, an impact mill, an expansion mill, a ball mill, a high-speed rotary projectile mill, and a high-speed rotary impact mill.
Preferably, the sintering temperature is 400-1000 ℃.
More preferably, the sintering temperature is 600-950 ℃.
Preferably, the sintering comprises sintering under one or more of air, vacuum, nitrogen, argon-hydrogen, oxygen atmospheres.
The invention also provides a lithium battery, which comprises the zinc-based pre-lithiation material.
Preferably, the preparation method of the positive electrode plate of the lithium battery comprises the following steps: mixing and homogenizing zinc-based pre-lithiation material, anode material, conductive agent and adhesive according to a certain mass ratio, then coating on an aluminum foil current collector, drying, rolling, and vacuum drying at 80-120 ℃ for 8-16 hours to obtain the anode sheet.
Compared with the existing pre-lithiated material, the zinc-based pre-lithiated material provided by the invention has the following advantages:
(1) Raw materials are simple and easy to obtain, the price is low, lithium sources such as lithium carbonate and lithium hydroxide are common lithium source materials, zinc sources such as zinc oxide and zinc carbonate are common cheap materials, and the synthesized materials have great advantages in price;
(2) The material synthesis method is simple, special environmental treatment is not needed, and large-scale amplification is easy;
(3) The raw material Zn has low molecular weight, and the zinc-based pre-lithium material Li xZnOy has very high theoretical capacity, so that the zinc-based pre-lithium material Li xZnOy is very suitable for being used as a pre-lithium material for lithium supplementation; meanwhile, after lithium removal by charging, the residual substances are mainly ZnO, which is an inorganic filling ceramic material commonly used for preparing polymer electrolyte, and the side effect of the battery is avoided.
(4) The preparation method of the zinc-based pre-lithiated material is simple, is compatible with the prior art, and is easy for industrial production.
[ Description of the drawings ]
FIG. 1 is a scanning electron microscope image of a prelithiated material provided in example 1 of the present invention;
Fig. 2 is a first week charging map of the prelithiated material provided in example 1 of the present invention.
[ Detailed description ] of the invention
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
Example 1 provides a zinc-based pre-lithium material Li 6ZnO4, which is prepared by weighing lithium hydroxide with the granularity of 500nm and zinc oxide with the granularity of 200nm according to the corresponding stoichiometric ratio, placing the two materials into a V-shaped conical screw mixer for high-speed mixing at the rotating speed of 400rpm for 3 hours; taking out the mixture, placing the mixture in a tube furnace, sintering the mixture at 850 ℃ in an argon atmosphere for 10 hours, and naturally cooling the mixture; crushing the sintered semi-finished product by using a jaw crusher, and crushing by using a jet mill to obtain the Li 6ZnO4 pre-lithiated material, wherein the morphology of the Li 6ZnO4 pre-lithiated material is shown in a Scanning Electron Microscope (SEM) diagram of FIG. 1.
Preparing a positive electrode plate: mixing a zinc-based pre-lithium material Li 6ZnO4, a conductive agent Super P and an adhesive PVDF according to a mass ratio of 80:10:10, wherein NMP is used as a dispersing agent; coating the obtained slurry on an aluminum foil current collector, wherein the coating thickness is 200um; the pole piece obtained is rolled, dried in vacuum at 110 ℃ for 12 hours, and cut into a round piece with the diameter of 12mm for standby.
And (3) assembling a button cell: a CR2032 button cell was assembled in a glove box filled with argon using 1.0mol/L LiPF 6 -EC/EMC (3:7v/v) as electrolyte, a 14mm diameter Li tab as the negative electrode, and a Cellgard-2400 separator.
Electrochemical testing: constant current charge and discharge mode test was performed using a charge and discharge instrument model CT2001A available from Wuhan blue Electron Co., ltd at 25℃in a voltage range of 2.5-4.6V and a current density of 50mAh/g. The first-week charge and discharge of the zinc-based pre-lithium material of example 1 is shown in fig. 2, and the result shows that the specific charge capacity, namely the delithiation capacity, is 760mAh/g, the voltage plateau is between 4.2 and 4.6V, the content contribution of the voltage range is higher, but the partial capacity is also between 3.5 and 4.2V, and the zinc-based pre-lithium material can also be used for materials with lower charge cut-off voltage.
Example 2
Example 2 provides a zinc-based pre-lithium material Li 4ZnO3, which is prepared by weighing lithium hydroxide with granularity of 1um and zinc oxide with granularity of 200nm according to corresponding stoichiometric ratio, placing the two materials into a ball mill for mixing, adding water as a dispersing machine, and carrying out revolution at 600rpm and rotation at 300rpm for 5 hours. Taking out the mixture, placing the mixture in a tube furnace, sintering the mixture at 900 ℃ in an argon atmosphere for 16 hours, and naturally cooling the mixture. Crushing the sintered semi-finished product by using a jaw crusher, crushing by using a jet mill to obtain a Li 4ZnO3 pre-lithiated material, and performing electrochemical test according to the method of example 1, wherein the specific charge capacity, namely the lithium removal capacity, is 480mAh/g.
Example 3
Example 3 provides a zinc-based pre-lithium material Li 2ZnO2 prepared by weighing lithium carbonate with a particle size of 1um and zinc oxide with a particle size of 500nm according to the corresponding stoichiometric ratio, placing the two materials in a V-cone screw mixer for high-speed mixing at a rotation speed of 400rpm for 2 hours. Taking out the mixture, placing the mixture in a muffle furnace, sintering the mixture at 900 ℃ in the air atmosphere for 12 hours, and naturally cooling the mixture. Crushing the sintered semi-finished product by using a jaw crusher, crushing by using a jet mill to obtain a Li 2ZnO2 pre-lithiated material, and performing electrochemical test according to the method of example 1, wherein the specific charge capacity is 310mAh/g.
Example 4
Example 4 provides a zinc-based pre-lithium material Li 4.8ZnO3.4, which is prepared by weighing lithium carbonate with a particle size of 500nm and zinc carbonate with a particle size of 500nm according to the corresponding stoichiometric ratio, mixing the two materials at high speed in a V-cone screw mixer at a rotation speed of 400rpm for 3 hours. Taking out the mixture, placing the mixture in a tube furnace, sintering the mixture at 900 ℃ in an argon atmosphere for 24 hours, and naturally cooling the mixture. Crushing the sintered semi-finished product by using a jaw crusher, crushing by using a jet mill to obtain a Li 4.8ZnO3.4 pre-lithiated material, and performing electrochemical test according to the method of example 1, wherein the specific charge capacity is 510mAh/g.
Example 5
Example 5 provides a zinc-based pre-lithium material Li 4.4ZnO3.2, which is prepared by weighing lithium hydroxide with a granularity of 2um and zinc carbonate with a granularity of 500nm according to corresponding stoichiometric ratio, mixing the two materials at high speed in a V-shaped conical screw mixer, wherein the rotating speed is 400rpm, and the mixing time is 3 hours. Taking out the mixture, placing the mixture in a tube furnace, sintering the mixture at 900 ℃ in a nitrogen atmosphere for 24 hours, and naturally cooling the mixture. Crushing the sintered semi-finished product by using a jaw crusher, crushing by using a jet mill to obtain a Li 4.4ZnO3.2 pre-lithiated material, and performing electrochemical test according to the method of example 1, wherein the specific charge capacity is 490mAh/g.
Example 6
Example 6 provides a zinc-based pre-lithium material Li 5.4ZnO3.7, which is prepared by weighing lithium acetate with a particle size of 500nm and zinc oxide with a particle size of 500nm according to the corresponding stoichiometric ratio, mixing the two materials at high speed in a V-cone screw mixer at a rotation speed of 400rpm for 2 hours. Taking out the mixture, placing the mixture in a tube furnace, sintering the mixture at 900 ℃ in an argon atmosphere for 24 hours, and naturally cooling the mixture. Crushing the sintered semi-finished product by using a jaw crusher, crushing by using a jet mill to obtain a Li 5.4ZnO3.7 pre-lithiated material, and performing electrochemical test according to the method of example 1, wherein the specific charge capacity is 720mAh/g.
Example 7
Example 7 provides a zinc-based pre-lithium material Li 2.2ZnO2.1, which is prepared by weighing lithium hydroxide with the granularity of 500nm and zinc oxide with the granularity of 200nm according to the corresponding stoichiometric ratio, placing the two materials into a V-shaped conical screw mixer for high-speed mixing at the rotating speed of 400rpm for 2 hours; taking out the mixture, placing the mixture in a tube furnace, sintering the mixture at 900 ℃ in an argon atmosphere for 24 hours, and naturally cooling the mixture; crushing the sintered semi-finished product by using a jaw crusher, crushing by using a jet mill to obtain a Li 2.2ZnO2.1 pre-lithiated material, and performing electrochemical test according to the method of example 1, wherein the specific charge capacity is 340mAh/g.
The higher the Li content, the higher the charging capacity, the better the lithium supplementing effect, but the higher the Li content, the worse the material stability, the higher the synthetic difficulty, and the material is easier to absorb water, which affects the post-homogenate coating. The comprehensive performance and cost are achieved, and the most suitable proportion is selected;
Example 8
The embodiment provides a carbon-coated zinc-based pre-lithium material Li 6ZnO4, which is marked as C-Li 6ZnO4, and the preparation method comprises the steps of mixing lithium hydroxide with the granularity of 500nm and zinc oxide with the granularity of 500nm in a V-shaped conical spiral mixer at a high speed according to the corresponding stoichiometric ratio, wherein the rotating speed is 400rpm, and the mixing time is2 hours; taking out the mixture, placing the mixture in a muffle furnace, sintering the mixture in the air at 900 ℃ for 12 hours, and naturally cooling the mixture; crushing the sintered semi-finished product by using a jaw crusher, and crushing by using a jet mill to obtain Li 6ZnO4; and mixing the obtained Li 6ZnO4 and the conductive graphite in a high-energy ball mill, wherein the revolution speed is 600rpm, the rotation speed is 300rpm, and the mixing time is 4 hours to obtain the carbon-coated pre-lithiated material C-Li 6ZnO4. The button cell was assembled and electrochemically tested as in example 1, with a specific charge capacity of 765mAh/g, and a slight increase in capacity compared to example 1, due to the carbon coating treatment of the sample, had better conductivity, and the kinetics of the electrochemical reaction was easier to carry out, facilitating the release of capacity.
Examples 9 to 14
Examples 9 to 14 are applications of zinc-based pre-lithiated materials in conventional positive electrode sheets, the zinc-based pre-lithiated materials used are Li 6ZnO4 or carbon-coated C-Li 6ZnO4 prepared by the methods of example 1 and example 8, and the positive electrode materials used include Lithium Cobalt Oxide (LCO), nickel cobalt aluminum ternary materials (NCA), nickel cobalt manganese ternary materials (NCM 523), as shown in table 1.
Preparing a positive electrode plate: mixing the prepared zinc-based pre-lithiated material, the positive electrode material, the conductive agent Super P and the adhesive PVDF according to the mass ratio of 10:80:5:5, wherein NMP is used as a dispersing agent; coating the obtained slurry on an aluminum foil current collector, wherein the coating thickness is 200um; the pole piece obtained is rolled, dried in vacuum at 110 ℃ for 12 hours, and cut into a round piece with the diameter of 12mm for standby.
And (3) assembling a button cell: a CR2032 button cell was assembled in a glove box filled with argon using 1.0mol/L LiPF6-EC/EMC (3:7v/v) as electrolyte, a 14mm diameter Li tab as the negative electrode, and Cellgard-2400 separator.
Electrochemical testing: the fabricated button cell was subjected to a constant current charge-discharge mode test using a charge-discharge meter available from the company, inc. of the electric electronics GmbH, model CT2001A, at a test temperature of 25℃and a charge current rate of 0.05 ℃.
The voltage ranges, and test results are shown in table 1, where control groups 1-3 are conventional button lithium batteries that do not employ pre-lithium materials.
According to the test result, on the premise that the positive electrode materials are the same, after the pre-lithium material is added, the first-week charging specific capacity of the button cell can be improved compared with that of a comparison group, and the carbon-coated pre-lithium material has better conductivity, better lithium supplementing effect and higher first-week charging specific capacity.
TABLE 1 test results for examples 9-14 and control groups 1-3
The above is a further detailed description of the invention in connection with specific preferred embodiments, and it is not to be construed as limiting the practice of the invention to these descriptions. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these shall be considered to be within the scope of the invention.
Claims (8)
1. The application of the zinc-based pre-lithiation material in improving the capacity of a lithium battery is characterized in that the structural general formula of the zinc-based pre-lithiation material is Li xZnOy, wherein x is more than or equal to 4 and less than or equal to 6, and y is more than or equal to 3 and less than or equal to 4; wherein the granularity of the zinc-based pre-lithiation material is between 50nm and 50um, and the delithiation capacity is between 400mAh/g and 950 mAh/g.
2. The carbon-coated zinc-based prelithiation material is characterized by being formed by compounding the zinc-based prelithiation material and a carbon material in the application of claim 1, and the structural general formula is as follows: C-Li xZnOy, wherein x is more than or equal to 4 and less than or equal to 6, and y is more than or equal to 3 and less than or equal to 4; wherein the granularity of the zinc-based pre-lithiation material is between 50nm and 50um, the delithiation capacity is between 400mAh/g and 950mAh/g, and the carbon material is uniformly or unevenly coated on the surface of the zinc-based pre-lithiation material; the mass ratio of the carbon material to the zinc-based pre-lithiated material is between 1:1000 and 1:20.
3. The carbon-coated zinc-based prelithiation material of claim 2, wherein the carbon material comprises one or more of amorphous carbon, graphene, carbon nanotubes, conductive graphite.
4. A method of preparing a zinc-based prelithiation material for use in accordance with claim 1, comprising the steps of: ball-milling and mixing a lithium source and a zinc source in a molar ratio of 2:1-6:1, sintering in sintering equipment, cooling to room temperature, and fully crushing the obtained material to obtain the zinc-based prelithiation material.
5. The method according to claim 4, wherein the lithium source is one or more of lithium carbonate, lithium hydroxide, and lithium acetate; the zinc source is one or more of zinc oxide, zinc carbonate and zinc acetate.
6. The preparation method according to claim 4 or 5, wherein the preparation method comprises weighing lithium hydroxide with particle size of 500nm and zinc oxide with particle size of 200nm according to corresponding stoichiometric ratio, placing the two materials into a V-cone screw mixer for high-speed mixing at 400rpm for 3 hours; taking out the mixture, placing the mixture in a tube furnace, sintering the mixture at 850 ℃ in an argon atmosphere for 10 hours, and naturally cooling the mixture; crushing the sintered semi-finished product by using a jaw crusher, and crushing by using a jet mill to obtain the Li 6ZnO4 pre-lithiated material.
7. The production method according to claim 4 or 5, wherein the production method comprises mixing lithium hydroxide having a particle size of 500nm and zinc oxide having a particle size of 500nm at a high speed in a V-cone spiral mixer at a rotation speed of 400rpm for 2 hours in accordance with the respective stoichiometric ratio; taking out the mixture, placing the mixture in a muffle furnace, sintering the mixture in the air at 900 ℃ for 12 hours, and naturally cooling the mixture; crushing the sintered semi-finished product by using a jaw crusher, and crushing by using a jet mill to obtain Li 6ZnO4; and mixing the obtained Li 6ZnO4 and the conductive graphite in a high-energy ball mill, wherein the revolution speed is 600rpm, the rotation speed is 300rpm, and the mixing time is 4 hours to obtain the carbon-coated pre-lithiated material C-Li 6ZnO4.
8. A lithium battery comprising the zinc-based pre-lithiated material of claim 1 in use and/or the carbon-coated zinc-based pre-lithiated material of any one of claim 2.
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| CN106711433A (en) * | 2015-11-18 | 2017-05-24 | 宁德新能源科技有限公司 | Lithium ion battery and anode plate thereof |
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