CN116598465A - High-rate lithium battery negative electrode material and preparation method thereof - Google Patents
High-rate lithium battery negative electrode material and preparation method thereof Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007773 negative electrode material Substances 0.000 title abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000498 ball milling Methods 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- 239000002699 waste material Substances 0.000 claims abstract description 20
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 16
- 239000010439 graphite Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 11
- 239000010432 diamond Substances 0.000 claims abstract description 11
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000010405 anode material Substances 0.000 claims description 15
- 239000010406 cathode material Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 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 10
- 239000008103 glucose Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 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 2
- 239000011294 coal tar pitch Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000011863 silicon-based powder Substances 0.000 abstract description 13
- 230000009471 action Effects 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 description 20
- 239000011149 active material Substances 0.000 description 15
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 6
- 239000010426 asphalt Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- -1 artificial graphite Chemical compound 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/58—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
Abstract
The invention provides a high-rate lithium battery negative electrode material and a preparation method thereof, wherein the lithium battery negative electrode material comprises 75-90% of graphite powder by weight; 0.05-5% by weight of metal powder; the rest is waste silicon mud of the monocrystalline silicon diamond wire; the method comprises the steps of mixing, ball milling, coating and the like. According to the invention, a mechanochemical method is adopted, under the action of mechanochemistry, silicon powder and metal powder are adopted to form a synergistic effect between the silicon powder and the metal powder, so that the conductivity is improved, meanwhile, the crystalline flake graphite is introduced, the crystalline flake graphite is wrapped through alloy, and the morphology of mechanochemical wrapping is controlled through controlling the ratio of the thickness to the diameter of the crystalline flake graphite.
Description
Technical Field
The invention relates to the field of lithium battery negative electrode materials, in particular to a high-rate lithium battery negative electrode material prepared from natural graphite spherical tailings and a preparation method thereof.
Background
The silicon-carbon anode is the best way for solving the problem of silicon anode expansion, not only reduces the negative effect caused by silicon expansion, but also greatly reduces the silicon anode, nanocrystallization, porosity and dopingAnd the cost is equal. However, in general, silicon carbon anodes encapsulate silicon particles, such as graphene, tar, biomass, C, with poorly conductive carbon materials 3 N 4 And the like, the negative electrode damage caused by silicon expansion is prevented, and the cycle life of the negative electrode is influenced. In addition, the silicon negative electrode has poor conductivity, and the rapid transmission of electrons and lithium ions is difficult to ensure, so that the silicon negative electrode has poor conductivity.
Studies have shown that incorporation of graphite, such as artificial graphite, into silicon carbon anodes increases their conductivity, but is limited by the crystalline orientation and conductivity of the graphite, which still results in poor rate performance. Therefore, various metals are added for research, silicon is coated by means of hydrogen reduction, electric reduction and the like, the metal compound can adapt to the volume change of silicon, the conductivity of the silicon-based composite material can be effectively improved due to the extremely high conductivity of the metal compound, and the volume expansion of the silicon can be effectively reduced to promote the transportation of lithium ions. In summary, in order to solve the conductivity problem of the silicon-carbon negative electrode, the addition of metals has reached consensus, but the key point is to see which method is more efficient, green and low cost. Some reports indicate that composites synthesized by chemical methods inevitably contain some residual impurities, affecting battery performance.
Disclosure of Invention
Aiming at the defects that the lithium battery cathode contains some residual impurities and affects the battery performance, the invention provides a high-rate lithium battery cathode material and a preparation method thereof.
The technical scheme for realizing the technical purpose of the invention is as follows: a high-rate lithium battery cathode material is prepared from the following materials:
(1) 75-90% of graphite powder;
(2) 0.05-5% by weight of metal powder;
(3) The rest is waste silicon mud of the monocrystalline silicon diamond wire;
the granularity of the waste silicon mud of the monocrystalline silicon diamond wire is 50-200 nanometers, the purity is 99.9%, and the moisture is less than 1%.
Further, in the high-rate lithium battery anode material, the following steps are included: the graphite powder is spherical tailing, crystalline flake graphite or artificial graphite.
Further, in the high-rate lithium battery anode material, the following steps are included: the metal powder is copper powder, nickel powder or aluminum powder, or any two of the metal powder and the aluminum powder are compounded.
The invention also provides a preparation method of the high-rate lithium battery anode material, which comprises the following steps:
step 1, preparing graphite powder, metal powder and waste silicon mud of monocrystalline silicon diamond wires according to a set proportion;
step 2, fully mixing the prepared graphite powder and metal powder to obtain a first mixture;
step 3, performing ball milling treatment on the first mixture to obtain a second mixture;
step 4, adding the prepared waste silicon mud of the monocrystalline silicon diamond wire into the second mixture, and continuing ball milling to obtain a third mixture;
step 5, coating the third mixture, wherein: carbonizing at a set temperature to obtain the high-rate lithium battery cathode material.
Further, the preparation method of the high-rate lithium battery anode material comprises the following steps: and (3) ball milling for 1-8 hours in the step (2).
Further, the preparation method of the high-rate lithium battery anode material comprises the following steps: the reagent used for coating in the step 5 is one or more of coal tar pitch, phenolic resin and glucose.
Further, the preparation method of the high-rate lithium battery anode material comprises the following steps: the carbonization temperature is 300-1200 ℃, and the heat preservation time is 10-120 min.
Further, the preparation method of the high-rate lithium battery anode material comprises the following steps: the carbonization atmosphere is an argon atmosphere, a nitrogen atmosphere or a hydrogen-argon mixed atmosphere with 5 percent of hydrogen.
According to the invention, a mechanochemical method is adopted, under the action of mechanochemistry, silicon powder and metal powder are adopted to form a synergistic effect between the silicon powder and the metal powder, so that the conductivity is improved, meanwhile, the crystalline flake graphite is introduced, the crystalline flake graphite is wrapped through alloy, and the morphology of mechanochemical wrapping is controlled through controlling the ratio of the thickness to the diameter of the crystalline flake graphite.
In addition, the method is simple to operate, the required modifier is a conventional cheap reagent, and the raw materials and the synthesis process are suitable for large-scale production, so that the prepared anode material has a great application prospect in lithium ion batteries.
The invention will be described in more detail below with reference to the drawings and examples.
Drawings
FIG. 1 is a process flow diagram of the present invention;
fig. 2 is an SEM image of the active material of embodiment 1 of the present invention: a) SEM image after active material doping; b) SEM images of doped metal active materials;
FIG. 3 is a graph showing a blue-doped electrical magnification test according to embodiment 1 of the present invention;
Detailed Description
Example 1 preparation of silicon carbon negative electrode Material
Placing the purified 89KG single crystal silicon diamond wire waste silicon mud and 10KG copper powder with the purity of 99.9% into a mortar to form a mixture, placing the mixture into a ball milling tank, wherein the ball milling speed of the ball milling tank is 400rpm, the ball milling time is 2h, adding 400KG flake graphite, continuing ball milling for 8h, sieving with a 200-mesh sieve, performing demagnetizing treatment to obtain a composite material, and then compositing the composite material with glucose, wherein the mass ratio of the composite material to the glucose is 95: and 5, fully mixing the two, coating the target product by glucose, wherein the carbonization temperature is 900 ℃, the time is 180min, and the protective atmosphere is argon. In the embodiment, the particle size of the flake graphite powder is 2-10 microns, the particle size of the copper powder is 5-20 microns, the type of the ball mill used is QXQM-4, the ball mill is 4L in specification, 360-degree omnibearing planetary turnover is realized, and the discharging granularity can reach 0.1 mu m; the special material precision gear is adopted, the operation is stable, safe and low in noise, and the overturning motor has a braking locking function.
A scanning electron microscope (JSM-7800) was used to observe the morphology of the modified natural graphite spherical tailing anode material under the above conditions, as shown in FIG. 2.
The silicon-carbon negative electrode material prepared in example 1 is directly used as a negative electrode material of a lithium ion battery, a metal lithium sheet is used as a counter electrode, celgard2325 is used as a diaphragm, 1mol/L LiPF6 (a solvent is a mixed solution of ethylene carbonate and dimethyl carbonate in a volume ratio of 1:1) is used as an electrolyte, a CR2032 type button battery shell is assembled into the button battery in a glove box protected by argon. In the blue-ray test program, the charge-discharge current density is 0.1A/g, 0.2A/g, 0.5A/g, 1.0A/g, 2.0A/g, 5.0A/g, 2.0A/g, 1.0A/g, 0.5A/g, 0.2A/g, 0.1A/g, the charge-discharge cycle times are 10 circles under the same current density, and the voltage charge-discharge interval is 0.01-3V. The charge-discharge cycle performance of the battery is shown in figure 3, when the current density is 0.1A/g, the specific capacity of the active material is 821.7 mA h/g, the specific capacity of the doped metal is 957.6 mA h/g, when the current density is 5.0A/g, the specific capacity of the active material is 172.9 mA h/g, the specific capacity of the doped metal is 262.8 mA h/g, the capacity retention rates are 21% and 27.4% respectively, and the cathode can still better maintain the small-current charge-discharge performance after heavy-current discharge. The modified cathode material has higher capacity and cycle stability.
Example 2
Placing purified waste silicon mud with a certain mass of monocrystalline silicon diamond wires and copper powder with the purity of 99.9% into a mortar to form a mixture, wherein the mass ratio of the waste silicon powder to the copper powder is 5:1, placing the mixture into a ball milling tank, wherein the rotating speed of the ball milling tank is 400rpm, the ball milling time is 2 hours, adding 80% of flake graphite, continuously ball milling for 8 hours, sieving by a 200-mesh sieve, performing demagnetizing treatment to obtain a composite material, and then compositing the composite material with coal asphalt, wherein the mass ratio of the composite material to the coal asphalt is 95: and 5, fully mixing the two materials, carbonizing at 700 ℃ for 120min under the protection of argon. The final material is assembled into a semi-button battery for charge and discharge performance test, when the current density is 0.1A/g, the specific capacity of the active material is 815.5 mA h/g, the specific capacity of the doped metal is 950.9 mA h/g, when the current density is 5.0A/g, the specific capacity of the active material is 169 mA h/g, the specific capacity of the doped metal is 263.9 mA h/g, the capacity retention rates are 20.7% and 27.75% respectively, and the cathode can still better maintain the small-current charge and discharge performance after large-current discharge. The modified cathode material has higher capacity and cycle stability.
Example 3
Placing the purified waste silicon powder with a certain mass and aluminum powder with the purity of 99.9% into a mortar to form a mixture, wherein the mass ratio of the waste silicon powder to the aluminum powder is 89:10, placing the mixture into a ball milling tank, wherein the rotating speed of the ball milling tank is 400rpm, the ball milling time is 2 hours, adding 80% of flake graphite, continuously ball milling for 8 hours, sieving with a 200-mesh sieve, performing demagnetizing treatment to obtain a composite material, and then compositing the composite material with glucose, wherein the mass ratio of the composite material to the glucose is 95: and 5, fully mixing the two, coating the target product by glucose, wherein the carbonization temperature is 700 ℃, the time is 120min, and the protective atmosphere is argon. The final material is assembled into a semi-button battery for charge and discharge performance test, when the current density is 0.1A/g, the specific capacity of the active material is 825.6 mA h/g, the specific capacity after doping metal is 956.8 mA h/g, when the current density is 5.0A/g, the specific capacity of the active material is 171.3 mA h/g, the specific capacity after doping metal is 263.1 mA h/g, the capacity retention rates are 20.7% and 27.49% respectively, and the cathode can still better maintain the small-current charge and discharge performance after high-current discharge. The modified cathode material has higher capacity and cycle stability.
Example 4
Placing the purified waste silicon powder with a certain mass and aluminum powder with the purity of 99.9% into a mortar to form a mixture, wherein the mass ratio of the waste silicon powder to the aluminum powder is 5:1, placing the mixture into a ball milling tank, wherein the rotating speed of the ball milling tank is 400rpm, the ball milling time is 2 hours, adding 80% of flake graphite, continuously ball milling for 8 hours, sieving by a 200-mesh sieve, performing demagnetizing treatment to obtain a composite material, and then compositing the composite material with coal asphalt, wherein the mass ratio of the composite material to the coal asphalt is 95: and 5, fully mixing the two materials, carbonizing at 900 ℃ for 180min under the protection of argon. The final material is assembled into a semi-button battery for charge and discharge performance test, when the current density is 0.1A/g, the specific capacity of the active material is 824.1 mA h/g, when the specific capacity of the doped metal is 956.9 mA h/g, the current density is 5.0A/g, the specific capacity of the active material is 172.5 mA h/g, the specific capacity of the doped metal is 261.9 mA h/g, the capacity retention rate is 20.9% and 27.3% respectively, and the cathode can still better maintain the small-current charge and discharge performance after heavy current discharge. The modified cathode material has higher capacity and cycle stability.
Example 5
Placing the purified waste silicon powder with a certain mass and nickel powder with the purity of 99.9% into a mortar to form a mixture, wherein the mass ratio of the waste silicon powder to the nickel powder is 89:10, placing the mixture into a ball milling tank, wherein the rotating speed of the ball milling tank is 400rpm, the ball milling time is 2 hours, adding 80% of flake graphite, continuously ball milling for 8 hours, sieving by a 200-mesh sieve, performing demagnetizing treatment to obtain a composite material, and then compositing the composite material with glucose, wherein the mass ratio of the composite material to the glucose is 95: and 5, fully mixing the two materials, carbonizing at 900 ℃ for 180min under the protection of argon. The final material is assembled into a semi-button battery for charge and discharge performance test, when the current density is 0.1A/g, the specific capacity of the active material is 822 mA h/g, the specific capacity after doping metal is 956.1 mA h/g, when the current density is 5.0A/g, the specific capacity of the active material is 173 mA h/g, the specific capacity after doping metal is 263.5 mA h/g, the capacity retention rate is 21% and 27.5% respectively, and the cathode can still better keep the small-current charge and discharge performance after heavy current discharge. The modified cathode material has higher capacity and cycle stability.
Example 6
Placing the purified waste silicon powder with a certain mass and nickel powder with the purity of 99.9% into a mortar to form a mixture, wherein the mass ratio of the waste silicon powder to the nickel powder is 5:1, placing the mixture into a ball milling tank, wherein the rotating speed of the ball milling tank is 400rpm, the ball milling time is 2 hours, adding 80% of flake graphite, continuously ball milling for 8 hours, sieving by a 200-mesh sieve, performing demagnetizing treatment to obtain a composite material, and then compositing the composite material with coal asphalt, wherein the mass ratio of the composite material to the coal asphalt is 95: and 5, fully mixing the two materials, carbonizing at 700 ℃ for 120min under the protection of argon. The final material is assembled into a semi-button battery for charge and discharge performance test, when the current density is 0.1A/g, the specific capacity of the active material is 820.7 mA h/g, when the specific capacity of the doped metal is 957.9 mA h/g, the current density is 5.0A/g, the specific capacity of the active material is 173.4 mA h/g, the specific capacity of the doped metal is 262.2 mA h/g, the capacity retention rates are 21.1% and 27.37% respectively, and the cathode can still better maintain the small-current charge and discharge performance after large-current discharge. The modified cathode material has higher capacity and cycle stability.
Claims (8)
1. A high-rate lithium battery cathode material is characterized in that: prepared from the following materials:
(1) 75-90% of graphite powder;
(2) 0.05-5% by weight of metal powder;
(3) The rest is waste silicon mud of the monocrystalline silicon diamond wire;
the granularity of the waste silicon mud of the monocrystalline silicon diamond wire is 50-200 nanometers, the purity is 99.9%, and the moisture is less than 1%.
2. The high-rate lithium battery anode material according to claim 1, characterized in that: the graphite powder is spherical tailing, crystalline flake graphite or artificial graphite.
3. The high-rate lithium battery anode material according to claim 1, characterized in that: the metal powder is copper powder, nickel powder or aluminum powder, or any two of the metal powder and the aluminum powder are compounded.
4. A preparation method of a high-rate lithium battery cathode material is characterized by comprising the following steps: the method comprises the following steps:
step 1, preparing graphite powder, metal powder and waste silicon mud of monocrystalline silicon diamond wires according to a set proportion;
step 2, fully mixing the prepared graphite powder and metal powder to obtain a first mixture;
step 3, performing ball milling treatment on the first mixture to obtain a second mixture;
step 4, adding the prepared waste silicon mud of the monocrystalline silicon diamond wire into the second mixture, and continuing ball milling to obtain a third mixture;
step 5, coating the third mixture, wherein: carbonizing at a set temperature to obtain the high-rate lithium battery cathode material.
5. The method for preparing the high-rate lithium battery anode material according to claim 4, which is characterized in that: in the step 3, the ball milling speed is 200-700 rpm, and the ball milling time is 1-10 h.
6. The method for preparing the high-rate lithium battery anode material according to claim 4, which is characterized in that: the reagent used for coating in the step 5 is one or more of coal tar pitch, phenolic resin and glucose.
7. The method for preparing the high-rate lithium battery anode material according to claim 6, which is characterized in that: the carbonization temperature is 300-1200 ℃, and the heat preservation time is 10-120 min.
8. The method for preparing the high-rate lithium battery anode material according to claim 6, which is characterized in that: the carbonization atmosphere is an argon atmosphere, a nitrogen atmosphere or a hydrogen-argon mixed atmosphere with 5 percent of hydrogen.
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