CN116495722B - A negative electrode material and its preparation method and application - Google Patents
A negative electrode material and its preparation method and application Download PDFInfo
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000010426 asphalt Substances 0.000 claims abstract description 23
- 239000010439 graphite Substances 0.000 claims abstract description 20
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 20
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 19
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000010298 pulverizing process Methods 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000005469 granulation Methods 0.000 claims description 17
- 230000003179 granulation Effects 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 15
- 239000003208 petroleum Substances 0.000 claims description 6
- 230000005347 demagnetization Effects 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims 1
- 238000010000 carbonizing Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 18
- 239000010405 anode material Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000005539 carbonized material Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- -1 helium Chemical compound 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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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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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
本发明涉及电池技术领域，具体而言，涉及一种负极材料及其制备方法和应用。本发明的负极材料的制备方法，包括以下步骤：将硅粉、二氧化钛和沥青的混合物进行热处理和粉碎处理，得到包覆料，将所述包覆料与石墨的混合物进行造粒和碳化处理。该方法简单易行，得到的负极材料循环性能优异，放电容量高。The present invention relates to the field of battery technology, and in particular, to a negative electrode material and a preparation method and application thereof. The preparation method of the negative electrode material of the present invention comprises the following steps: heat-treating and pulverizing a mixture of silicon powder, titanium dioxide and asphalt to obtain a coating material, and granulating and carbonizing the mixture of the coating material and graphite. The method is simple and easy to implement, and the obtained negative electrode material has excellent cycle performance and high discharge capacity.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a negative electrode material, and a preparation method and application thereof.
Background
The lithium ion battery is widely applied and researched by virtue of the advantages of high working voltage, high energy density, good safety performance, no pollution and the like. The lithium ion battery generally comprises a positive electrode material, a negative electrode material, a diaphragm, an electrolyte and the like, wherein the negative electrode material mainly uses carbon as a material. However, the theoretical specific capacity is lower and is 372mAh/g, and the future development space is limited, so that the preparation method is important for the development of the mixed anode material.
At present, the main stream in the market is mainly graphite, but the graphite has defects and side reactions, the silicon-carbon negative electrode is an important path for improving the energy density of a lithium battery, the theoretical specific capacity of silicon is 4200mAh/g, which is tens times of that of the graphite negative electrode, the lithium-removing potential of the silicon negative electrode is relatively low (0.4V), but the silicon negative electrode is large in volume expansion in the circulating process, and is 320% in volume expansion after full lithium intercalation, so that the silicon negative electrode is easy to be chalking and invalid in the lithium-removing process, and the coating and carbonization technology can modify the negative electrode material to reduce the expansion of the silicon negative electrode.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method of a negative electrode material, which solves the technical problems of low cycle performance, low discharge capacity and the like of a lithium ion battery prepared from the negative electrode material in the prior art.
The invention also aims to provide the anode material prepared by the preparation method of the anode material.
Another object of the present invention is to provide a negative electrode sheet including the negative electrode material.
Another object of the present invention is to provide a battery including the negative electrode sheet.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
a preparation method of a negative electrode material comprises the following steps:
and carrying out heat treatment and crushing treatment on the mixture of silica powder, titanium dioxide and asphalt to obtain a coating material, and granulating and carbonizing the mixture of the coating material and graphite.
Preferably, the grain diameter D50 of the silicon powder is less than or equal to 0.2 mu m.
Preferably, the particle diameter D50 of the titanium dioxide is less than or equal to 0.2 mu m.
Preferably, the particle diameter D50 of the graphite is 8-20 μm.
Preferably, the mass ratio of the silicon powder to the titanium dioxide to the asphalt is (0.1-1): (0.05-0.5): 1, preferably (0.3-0.8): (0.1-0.4): 1.
Preferably, the mass ratio of the graphite to the coating material is 1 (0.05-0.15), and preferably 1 (0.09-0.12).
Preferably, the bitumen comprises petroleum bitumen.
Preferably, the temperature of the heat treatment is 150-200 ℃, and the time of the heat treatment is 2-6 hours.
Preferably, the temperature of the heat treatment is 180-190 ℃, and the time of the heat treatment is 3-4 hours.
Preferably, the crushing treatment is performed until the particle diameter D50 of the coating material is 1-3 μm.
Preferably, the granulating temperature is 200-600 ℃, and the granulating time is 2-6 hours.
Preferably, the granulating temperature is 300-400 ℃, and the granulating time is 3-4.5 h.
Preferably, the carbonization temperature is 1000-1400 ℃, and the carbonization time is 6-16 h.
Preferably, the carbonization temperature is 1100-1300 ℃, and the carbonization time is 7-10 h.
According to the preparation method of the anode material, the material obtained after granulation is subjected to second crushing treatment.
Preferably, the carbonized material is subjected to a third pulverization treatment, a sieving treatment and a demagnetization treatment in this order.
Preferably, the heat treatment and the granulation are performed under a protective gas condition, respectively.
The negative electrode material prepared by the preparation method of the negative electrode material.
A negative electrode sheet comprising the negative electrode material.
A battery comprises the negative plate.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method of the anode material is simple and feasible, and the obtained anode material has excellent cycle performance and high discharge capacity.
(2) The cathode is made of cathode materials to improve electrochemical performance, and the prepared battery has the advantages of high discharge capacity and high cycle performance.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. 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.
According to one aspect, the present invention relates to a method for preparing a negative electrode material, comprising the steps of:
and carrying out heat treatment and crushing treatment on the mixture of silica powder, titanium dioxide and asphalt to obtain a coating material, and granulating and carbonizing the mixture of the coating material and graphite.
In the invention, the anatase titanium dioxide (TiO 2) has the properties of low expansion rate, high mechanical stability, high electron ion transmission property during lithium intercalation and lithium deintercalation, excellent electrochemical reversibility and the like, so that the anatase titanium dioxide has good coating potential. The TiO 2 layer with high crystallinity has compactness and uniformity, can improve interface stability, can be used as a buffer layer to effectively reduce impact damage of internal stress to a structure, can provide a high-efficiency transmission channel to accelerate ion and electron transfer, improves electrode dynamics behavior, can be used as a protective layer to obviously improve side reaction energy barrier to enhance side reaction resistance, and can also improve the overall safety of an electrode. The nano titanium dioxide layer is coated, so that a shell structure is formed, and the titanium dioxide effectively prevents graphite from expanding. According to the invention, through specific operation steps, the anode material with high discharge capacity and excellent cycle performance can be obtained.
Preferably, the grain diameter D50 of the silicon powder is less than or equal to 0.2 mu m. In one embodiment, particle size D50 of the silicon powder includes, but is not limited to, 0.01 μm, 0.02 μm, 0.03 μm, 0.04 μm, 0.05 μm, 0.06 μm, 0.07 μm, 0.08 μm, 0.09 μm, 0.1 μm, 0.11 μm, 0.15 μm, 0,16 μm, or 0.18 μm.
Preferably, the particle diameter D50 of the titanium dioxide is less than or equal to 0.2 mu m. In one embodiment, the particle size D50 of the titanium dioxide includes, but is not limited to, 0.01 μm, 0.02 μm, 0.03 μm, 0.04 μm, 0.05 μm, 0.06 μm, 0.07 μm, 0.08 μm, 0.09 μm, 0.1 μm, 0.11 μm, 0.15 μm, 0,16 μm, or 0.18 μm.
Preferably, the particle diameter D50 of the graphite is 8-20 μm. The particle size D50 of the graphite includes, but is not limited to, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm.
Preferably, the mass ratio of the silicon powder to the titanium dioxide to the asphalt is (0.1-1): (0.05-0.5): 1. Preferably (0.3 to 0.8): 0.1 to 0.4): 1.
In one embodiment, the mass ratio of the silica fume, the titanium dioxide, and the pitch includes, but is not limited to, 0.1:0.08:1, 0.5:0.4:1, 1:0.5:1. According to the invention, the silicon powder, the titanium dioxide and the asphalt are in a proper mass ratio, so that the electrochemical performance of the coating material can be improved, and the anode material obtained by compounding the coating material with graphite in the later stage has excellent multiplying power performance and cycle performance.
Preferably, the mass ratio of the graphite to the coating material is 1 (0.05-0.15), and preferably 1 (0.09-0.12). In one embodiment, the mass ratio of the graphite to the cladding material includes, but is not limited to, 1:0.06, 1:0.08, 1:0.1, 1:0.12, 1:0.14. In the invention, the mass ratio of the graphite to the coating material is in a proper range, so that the cathode material with high cycle performance and high rate performance can be obtained. If the ratio of the amount is too high or too low, a negative electrode material excellent in cycle performance and rate performance cannot be obtained.
Preferably, the bitumen comprises petroleum bitumen. Petroleum asphalt is a product of crude oil processing, and is black or blackish brown viscous liquid, semisolid or solid at normal temperature, and mainly contains hydrocarbons and non-hydrocarbon derivatives which are soluble in trichloroethylene. In one embodiment, the petroleum asphalt is medium temperature petroleum asphalt.
Preferably, the temperature of the heat treatment is 150-200 ℃, and the time of the heat treatment is 2-6 hours.
In one embodiment, the temperature of the heat treatment includes, but is not limited to, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 180 ℃, 185 ℃, 190 ℃, or 195 ℃. The time of the heat treatment includes, but is not limited to, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, or 5.5h. The invention improves the performance of the coating material by matching proper heat treatment temperature and heat treatment time.
Preferably, the temperature of the heat treatment is 180-190 ℃, and the time of the heat treatment is 3-4 hours. By further preferably heat treating temperature and time, the electrochemical properties of the anode material are further improved.
Preferably, the crushing treatment is performed until the particle diameter D50 of the coating material is 1-3 μm. In one embodiment, the comminuting treatment comminuting to a particle size D50 of the coating includes, but is not limited to, 1.2 μm, 1.5 μm, 1.7 μm, 2 μm, 2.2 μm, 2.5 μm, 2.7 μm, or 2.9 μm.
Preferably, the granulating temperature is 200-600 ℃, and the granulating time is 2-6 hours. In one embodiment, the temperature of the granulation includes, but is not limited to, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 300 ℃, 320 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, or 550 ℃. The granulating time comprises, but is not limited to, 2.5 hours, and the invention can further improve the cycle performance and discharge gram capacity of the cathode material by adopting the proper granulating temperature and time.
Preferably, the granulating temperature is 300-400 ℃, and the granulating time is 3-4.5 h.
Preferably, the carbonization temperature is 1000-1400 ℃, and the carbonization time is 6-16 h. In one embodiment, the temperature of the carbonization includes, but is not limited to 1050 ℃, 1100 ℃, 1120 ℃, 1150 ℃, 1180 ℃, 1200 ℃, 1220 ℃, 1250 ℃, 1280 ℃, 1300 ℃, 1340 ℃, or 1380 ℃. The carbonization time includes, but is not limited to, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, or 15h.
The carbonization treatment is performed in a box-type atmosphere furnace.
Preferably, the carbonization temperature is 1100-1300 ℃, and the carbonization time is 7-10 h.
Preferably, the material obtained after granulation is subjected to a second comminution treatment.
Preferably, the carbonized material is subjected to a third pulverization treatment, a sieving treatment and a demagnetization treatment in this order.
Preferably, the heat treatment and the granulation are performed under a protective gas condition, respectively.
The shielding gas includes nitrogen, inert gas such as helium, etc.
According to another aspect of the invention, the invention relates to a negative electrode material prepared by the preparation method of the negative electrode material.
According to another aspect, the invention relates to a negative electrode sheet comprising the negative electrode material.
According to another aspect, the present invention relates to a battery including the negative electrode sheet.
The present invention will be further explained below with reference to specific examples and comparative examples.
Example 1
A preparation method of a negative electrode material comprises the following steps:
Sanding silicon powder with the grain diameter D50 of 0.15 mu m and TiO 2 to the grain size D50 of 0.18 mu m, uniformly mixing the silicon powder, tiO 2 and asphalt in a mass ratio of 0.5:0.5:1, carrying out high-temperature mixing for 3 hours at 150 ℃ under nitrogen atmosphere, carrying out air current crushing after cooling to prepare a coating material with the grain diameter D50 of 2.0 mu m, carrying out high-temperature granulation for 4 hours with graphite powder in a mass ratio of 1:0.1 under 550 ℃ nitrogen atmosphere, carrying out high-temperature carbonization for 16 hours in a box-type atmosphere furnace at 1150 ℃ after the crushing of the graphite powder, and sieving and demagnetizing to prepare the lithium ion battery mixed cathode material.
Example 2
A preparation method of a negative electrode material comprises the following steps:
sanding silicon powder with the grain diameter D50 of 0.2 mu m and TiO 2 until the grain size D50 is 150nm, uniformly mixing the silicon powder, tiO 2 and asphalt according to the mass ratio of 0.1:0.05:1, carrying out high-temperature mixing for 6 hours under the nitrogen atmosphere at 180 ℃, carrying out air current crushing after cooling to prepare a coating material with the grain diameter D50 of 1.9 mu m, carrying out high-temperature granulation for 3 hours under the nitrogen atmosphere at 600 ℃ with the mass ratio of 1:0.05 with graphite fragments, carrying out high-temperature carbonization for 12 hours under the 1300 ℃ in a box-type atmosphere furnace after scattering, and preparing the lithium ion battery mixed cathode material.
Example 3
A preparation method of a negative electrode material comprises the following steps:
Sanding silicon powder with the grain diameter D50 of 0.10 mu m and TiO 2 until the grain size D50 is 200nm, uniformly mixing the silicon powder, tiO 2 and asphalt in a mass ratio of 0.3:0.2:1, carrying out high-temperature mixing for 4 hours at 200 ℃ under nitrogen atmosphere, reducing the temperature, carrying out jet milling to prepare a coating material with the grain diameter D50 of 2.1 mu m, carrying out high-temperature granulation for 6 hours with graphite powder in a mass ratio of 1:0.15 under 400 ℃ and nitrogen atmosphere, scattering the crushed D50 of 15 mu m, carrying out high-temperature carbonization for 12 hours at 1100 ℃ in a box-type atmosphere furnace, and sieving and demagnetizing to prepare the lithium ion battery mixed cathode material.
Comparative example 1
A preparation method of a negative electrode material comprises the following steps of removing silicon powder, tiO 2 and asphalt in a mass ratio of 0.03:0.02:1.95, and the other conditions are the same as in example 1.
Comparative example 2
A preparation method of a negative electrode material is the same as in example 1 except that the mass ratio of graphite particles to coating material is 1:0.03.
Comparative example 3
A preparation method of a negative electrode material, except that the temperature of high-temperature mixing is 130 ℃, the time is 1.5h, and other conditions are the same as in example 1.
Comparative example 4
A preparation method of a negative electrode material, except that the high temperature granulation temperature is 180 ℃, the time is 1.5h, and other conditions are the same as in example 1.
Comparative example 5
A preparation method of a negative electrode material, except that the high temperature carbonization temperature is 900 ℃ and the time is 5 hours, the other conditions are the same as in example 1.
Experimental example
The negative electrode materials of examples and comparative examples were prepared to obtain batteries, and the preparation method includes the steps of:
(1) Adding CMC solution with the weight percent of 1.5 and SP with the weight percent of 2000r/min into a high-speed dispersing machine, stirring for 10min, regulating the speed to 200r/min, adding the negative electrode material, stirring for 90min with the speed of 2000r/min, adding SBR solution with the weight percent of 50%, stirring for 10min, sieving, coating and coating the mixture with the thickness of 150 mu m, wherein the mass ratio of the components is that the negative electrode material is CMC, the SP is SBR=93:1.5:2.0:3.5.
(2) Drying, namely drying for 2 hours at 110 ℃ after drying for 4 hours at 60 ℃ by blowing.
(3) And (3) weighing the rolled cut pieces, namely adjusting a roller press, controlling the compaction density of the pole pieces to be more than 1.5g/cm 3, cutting the pole pieces into pole pieces with the diameter of 14mm, weighing, and then vacuum drying for 4 hours.
(4) And (3) assembling, namely weighing the pole pieces again, and assembling in a glove box, wherein the assembling sequence is that a negative electrode shell, 1 drop of electrolyte, the pole pieces, 3 drops of electrolyte, the diaphragm, 3 drops of electrolyte, the lithium pieces, the gaskets, the elastic pieces, the positive electrode shell and sealing.
(5) Blue electric test procedure 0.05C, 0.05mA 0.02mA discharge, 0.1C charge.
The obtained battery was subjected to performance test, and the results are shown in table 1.
TABLE 1 Performance test results
| Examples and comparative examples | Gram capacity (mAh/g) | First effect (%) |
| Example 1 | 375 | 93.5 |
| Example 2 | 370 | 93.7 |
| Example 3 | 380 | 93.8 |
| Comparative example 1 | 352 | 93.1 |
| Comparative example 2 | 355 | 93.3 |
| Comparative example 3 | 353 | 93.2 |
| Comparative example 4 | 356 | 93.0 |
| Comparative example 5 | 352 | 92.9 |
As shown in Table 1, the negative electrode material obtained by the specific operation steps and parameter conditions has excellent capacity, and the battery prepared from the negative electrode material has excellent cycle performance. The mass ratio of the silicon powder, the TiO 2 and the asphalt in the comparative example 1 is not in the protection scope of the invention, the mass ratio of the graphite powder to the cladding in the comparative example 2 is not in the protection scope of the invention, the temperature and the time of high-temperature mixing in the comparative example 3 are not in the protection scope of the invention, the temperature and the time of high-temperature granulation in the comparative example 4 are not in the protection scope of the invention, the temperature and the time of high-temperature carbonization in the comparative example 5 are not in the protection scope of the invention, and the capacity of the obtained anode material is poorer than that of the example 1.
It should be noted that the above embodiments are merely for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the technical solution described in the above embodiments may be modified or some or all of the technical features may be equivalently replaced, and these modifications or substitutions do not deviate from the essence of the corresponding technical solution from the scope of the technical solution of the embodiments of the present invention.
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