CN114520328A - Lithium ion battery cathode material, preparation thereof, cathode and battery - Google Patents
Lithium ion battery cathode material, preparation thereof, cathode and battery Download PDFInfo
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- CN114520328A CN114520328A CN202011312113.7A CN202011312113A CN114520328A CN 114520328 A CN114520328 A CN 114520328A CN 202011312113 A CN202011312113 A CN 202011312113A CN 114520328 A CN114520328 A CN 114520328A
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- carbon powder
- asphalt
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- 239000010406 cathode material Substances 0.000 title claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000010426 asphalt Substances 0.000 claims abstract description 33
- 239000007773 negative electrode material Substances 0.000 claims abstract description 25
- 239000011229 interlayer Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000002028 Biomass Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 89
- 239000000243 solution Substances 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 30
- 239000012300 argon atmosphere Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 238000009656 pre-carbonization Methods 0.000 claims description 12
- 239000011258 core-shell material Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000003208 petroleum Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 244000060011 Cocos nucifera Species 0.000 claims description 9
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 239000010410 layer Substances 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229940113088 dimethylacetamide Drugs 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 244000018633 Prunus armeniaca Species 0.000 claims description 4
- 235000009827 Prunus armeniaca Nutrition 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 240000007049 Juglans regia Species 0.000 claims description 3
- 235000009496 Juglans regia Nutrition 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 235000020234 walnut Nutrition 0.000 claims description 3
- 244000144730 Amygdalus persica Species 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 235000006040 Prunus persica var persica Nutrition 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- MLIKRVBXLNTXKF-UHFFFAOYSA-N ethoxyphosphonamidous acid Chemical compound CCOP(N)O MLIKRVBXLNTXKF-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 150000008300 phosphoramidites Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000011257 shell material Substances 0.000 claims 6
- 238000010000 carbonizing Methods 0.000 abstract description 10
- 239000007784 solid electrolyte Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000002427 irreversible effect Effects 0.000 abstract description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 16
- 238000001816 cooling Methods 0.000 description 10
- 238000007873 sieving Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 229910021385 hard carbon Inorganic materials 0.000 description 7
- 238000007600 charging Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 4
- 239000002194 amorphous carbon material Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000008096 xylene Substances 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
- H01M4/58—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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- H01M4/13—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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A lithium ion battery cathode material and preparation and application thereof are prepared by pre-carbonizing a biomass raw material, removing impurities, coating asphalt and carbonizing the biomass raw material to form a structure with larger internal disordered interlayer spacing and graphite-like characteristics on the outside. The negative electrode material can meet the requirement of rapid charge and discharge in an electrode, and realizes the high-rate performance of the negative electrode material; but also reduce irreversible capacity loss caused by excessive formation of solid electrolyte interfacial film, and has higher first cycle coulombic efficiency.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a negative electrode material for a high-specific-power lithium ion battery and a preparation method thereof.
Background
Lithium ion batteries are widely applied to industries such as consumer electronics, electric vehicles and large-scale energy storage as the mainstream secondary battery technology at present, and the life of human beings is greatly improved. With the change of application environment, lithium ion batteries are increasingly required to have rapid charging and discharging capabilities, such as start-stop batteries for automobiles, high-speed rails and subways, and model airplane batteries for unmanned aerial vehicles.
The lithium ion battery is required to complete electrochemical reaction in a very short time due to rapid charge and discharge performance. Therefore, the requirements for electron and ion transmission are high, and particularly, the transmission speed of lithium ions at the negative electrode and nearby is a key factor for limiting the high specific power of the lithium ions. Currently, the commercially available negative electrode materials include graphite, amorphous carbon materials, lithium titanate, and the like. The specific capacity of the graphite can reach more than 300 mA.h/g, the first cycle coulombic efficiency can reach more than 90%, but the graphite material has the problems of poor structural stability and poor compatibility with electrolyte, and is easy to generate a co-intercalation reaction with a propylene carbonate organic solvent in the electrolyte in the charging and discharging process to cause structural damage, so that the cycle stability and the charging and discharging efficiency of the battery are influenced. And due to the anisotropic structure characteristics of graphite, the free diffusion of lithium ions in the graphite structure is limited, and the interlayer spacing is small, so that the rate capability of the graphite cathode material is influenced. The amorphous carbon material mainly comprises hard carbon and soft carbon, compared with graphite, the amorphous carbon material is low in crystallinity, micropores exist, a lamellar structure is not as regular and ordered as graphite, a repeated graphite lamellar structure is generally lower than 2-3 layers, Li & lt + & gt can be embedded and separated from the material from various angles due to the mutually staggered lamellar structure, the interlayer distance is large, the rapid diffusion of lithium ions is facilitated, and the rapid charge and discharge of the material can be realized. The phenomena of solvent co-intercalation and obvious lattice expansion and contraction which are easily caused by graphite materials can not occur, and the hard carbon and soft carbon materials have the advantage of good cycle performance. In addition, the processing process does not need graphitization treatment, so the cost is obviously lower compared with that of graphite-based negative electrode materials. However, the first cycle efficiency of such materials is low (40-60%). How to realize high specific power discharge and high first-efficiency simultaneously is the key of high-rate charge and discharge batteries.
Disclosure of Invention
Aiming at the problem of low first cycle coulombic efficiency of the existing hard carbon material taking biomass as a raw material, the invention provides a cathode material for a high-specific power lithium ion battery, which is a carbon material and has a core-shell structure, wherein the particle size of an internal core is 3-8 mu m, and the interlayer spacing of 002 crystal planes is 0.37-0.41 nm; the thickness of the outer shell is 10-1000nm, and the spacing between 002 crystal planes is 0.34-0.36 nm. The method can not only meet the requirement of rapid charge and discharge in the electrode, but also realize the solid electrolyte interface film with compact cathode outside. The battery negative electrode material is particles with micron-scale particle size, which are formed by tightly combining the inside and the outside. The invention also provides a preparation method of the anode material, which is as follows, but not limited to the following steps:
1) drying and crushing a biomass raw material, and then carrying out pre-carbonization treatment for 1-3h at 500-800 ℃ in an inert atmosphere to obtain a product A;
2) sequentially putting the product A into NaOH solution and acid solution, soaking, stirring and cleaning (the cleaning aims at removing impurities except carbon in the raw material (the impurities comprise silicon, metal elements and the like)), then filtering, washing to be neutral, drying, and crushing by a jet mill to obtain carbon powder B with the particle size of 3-8 mu m;
3) and (2) carrying out asphalt coating treatment on the carbon powder B, and specifically comprising the steps of soaking the carbon powder B into a solvent (so that the carbon powder is completely soaked by the solvent), taking out the carbon powder adsorbed with the solvent, heating the asphalt to 210-350 ℃, adding the solvent, stirring to prepare a mixed solution, adding the carbon powder adsorbed with the solvent into an asphalt solution while stirring, drying, and carrying out carbonization treatment at 1100-1300 ℃ for 1-3h in an inert atmosphere to obtain the cathode material.
Wherein,
the biomass raw material is one or more than two of coconut shell, peach shell, apricot shell and walnut shell.
The inert atmosphere in the steps 1) and 3) is nitrogen atmosphere and/or argon atmosphere respectively;
the concentration of the NaOH solution in the step 2) is 1-5mol/L, and the acid solution is a hydrochloric acid solution, a sulfuric acid solution or a nitric acid solution, and the concentration is 1-5 mol/L; the dipping and stirring time is 1-100h, preferably 25-50 h; the temperature range during stirring is 25-70 ℃, preferably 50-70 ℃.
The asphalt is petroleum asphalt with a softening point of 200-250 ℃. Heating asphalt to a temperature higher than the softening point of the asphalt by 10-50 ℃, adding a solvent, and stirring to prepare a mixed solution, wherein the mass fraction of the asphalt solution is 30-50%.
The solvent is one or more than two of N-methyl pyrrolidone, dimethyl acetamide, hexamethyl phosphoramidite, hexa ethyl phosphoramidite and diphenyl ether.
The mass ratio of the carbon powder B to the asphalt is 6/4-8/2.
The invention also provides a lithium ion battery cathode, and the active material of the cathode is the material.
The invention also provides a lithium ion battery, and the negative electrode of the lithium ion battery is the negative electrode.
The invention has the following advantages:
(1) the cathode material provided by the invention has a hard carbon structure inside, has large interlayer spacing, is beneficial to the diffusion of lithium ions in the cathode material, can meet the requirement of rapid charge and discharge inside an electrode, and realizes the high rate performance of the cathode material.
(2) The outer surface of the cathode material provided by the invention has the graphite-like characteristic, the conductivity is good, the resistance of the cathode can be reduced, and the realization of the high rate performance of the cathode material is facilitated.
(3) The hard carbon material of the negative electrode material provided by the invention has a lower specific surface area, can reduce irreversible capacity loss caused by excessive formation of a solid electrolyte interface film, and has higher first-cycle coulombic efficiency.
Detailed Description
The present invention is described in detail below with reference to specific examples.
The prepared negative electrode material is used for button cell testing, and the cell testing method in the embodiment and the comparative example is the same, and specifically comprises the following steps: mixing the prepared negative electrode material, a conductive agent and polyvinylidene fluoride according to a ratio of 90: 2: 8, and uniformly mixing and dispersing the mixture into the N-methyl pyrrolidone. Coating the copper foil surface to form an electrode plate containing 3 +/-0.3 mg of negative electrode material per square centimeter of copper foil. Punching the electrode plate into a wafer, forming a battery structure with a sandwich structure together with a diaphragm and metal lithium, and adding an electrolyte (the concentration of lithium hexafluorophosphate is 1mol/L, the solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate (the volume ratio is 1: 1: 1), and the electrolyte additionally contains 2% of vinylene carbonate). The CCCV charging and discharging method is used for testing the battery performance, namely, the current is charged to 0V at 0.1C, then the constant voltage charging is stopped until 0.02C, then the discharging is stopped at 0.1C until 1.5V, one cycle is adopted, the first cycle coulomb efficiency of the negative electrode material is obtained by utilizing the discharging capacity to the charging capacity and is recorded in the table 1, then the charging and discharging are carried out at the currents of 1C, 2C and 5C, the cut-off voltage is 0V-1.5V, 5 cycles are operated at each current, and the average value is recorded in the table 1.
Example 1
Drying 1kg of coconut shell in a vacuum drying oven at 110 ℃ for 8h, crushing by a crusher, and carrying out pre-carbonization treatment under argon atmosphere, wherein the heat treatment temperature is 500 ℃ and the time is 2 h; then putting the carbon powder into 1M NaOH solution for ultrasonic cleaning for 2h, then putting the carbon powder into 2M hydrochloric acid solution for ultrasonic cleaning for 2h, washing the carbon powder with deionized water after filtering until the pH value is 7, drying the carbon powder at 110 ℃, and then crushing the carbon powder by using a jet mill to obtain carbon powder with the particle size of 3-8 mu M; adding 100g of carbon powder into N-methyl pyrrolidone for soaking for 5 hours, and taking out; heating 25g of petroleum asphalt with the softening point of 200 ℃ to 220 ℃, adding 50ml of N-methyl pyrrolidone, stirring to prepare a mixed solution, adding carbon powder adsorbed with the N-methyl pyrrolidone into the asphalt solution while stirring, drying, carbonizing at 1100 ℃ for 2h in an argon atmosphere, cooling to room temperature, crushing and sieving to obtain the cathode material with the core-shell structure, wherein the particle size of the core is 3-8 mu m, the spacing between 002 crystal planes is 0.38nm, the thickness of the shell is 100-500nm, and the spacing between 002 crystal planes is 0.35 nm.
The cathode material is made into a button cell, the button cell is subjected to cell performance detection, the charge-discharge reversible capacity of the cell is 382mAh/g, the first cycle coulomb efficiency is 80.6%, and the reversible capacity at the multiplying power performance of 5C/the reversible capacity at 0.1C is 69.9%.
Comparative example 1
Drying 1kg of coconut shell in a vacuum drying oven at 110 ℃ for 8h, crushing by a crusher, and carrying out pre-carbonization treatment under argon atmosphere, wherein the heat treatment temperature is 500 ℃ and the time is 2 h; then putting the carbon powder into 1M NaOH solution for ultrasonic cleaning for 2h, then putting the carbon powder into 2M hydrochloric acid solution for ultrasonic cleaning for 2h, washing the carbon powder with deionized water after filtering until the pH value is 7, drying the carbon powder at 110 ℃, and then crushing the carbon powder by using a jet mill to obtain carbon powder with the particle size of 3-8 mu M; and then carbonizing the obtained product in an argon atmosphere at 1100 ℃ for 2 hours, cooling to room temperature, crushing and sieving to obtain the negative electrode material with the particle size of 3-8 mu m and the 002 crystal plane interlayer spacing of 0.38 nm. The cell was prepared and the properties are shown in table 1.
Comparative example 2
Drying 1kg of coconut shell in a vacuum drying oven at 110 ℃ for 8h, crushing by a crusher, and carrying out pre-carbonization treatment under argon atmosphere, wherein the heat treatment temperature is 500 ℃ and the time is 2 h; then crushing by using a jet mill to obtain carbon powder with the particle size of 3-8 mu m; and then carbonizing the obtained product in an argon atmosphere at 1100 ℃ for 2 hours, cooling to room temperature, crushing and sieving to obtain the negative electrode material with the particle size of 3-8 mu m and the 002 crystal plane interlayer spacing of 0.38 nm. The cell was prepared and the properties are shown in table 1.
Comparative example 3
Drying 1kg of petroleum asphalt with a softening point of 200 ℃ in a vacuum drying oven at the temperature of 110 ℃ for 8h, then carrying out pre-carbonization treatment in an argon atmosphere at the temperature of 500 ℃ for 2h, and then crushing by using a jet mill to obtain carbon powder with the particle size of 3-8 mu m; then carbonizing the obtained product in argon atmosphere at 1100 ℃ for 2h, cooling to room temperature, pulverizing, and sieving to obtain a negative electrode material with a particle size of 3-8 μm and a 002 crystal plane interlayer spacing of 0.35 nm. The cell was prepared and the properties are shown in table 1.
Comparative example 4
Drying 1kg of coconut shell in a vacuum drying oven at 110 ℃ for 8h, crushing by a crusher, and carrying out pre-carbonization treatment under argon atmosphere, wherein the heat treatment temperature is 500 ℃ and the time is 2 h; then putting the carbon powder into 1M NaOH solution for ultrasonic cleaning for 2h, then putting the carbon powder into 2M hydrochloric acid solution for ultrasonic cleaning for 2h, washing the carbon powder with deionized water after filtering until the pH value is 7, drying the carbon powder at 110 ℃, and then crushing the carbon powder by using a jet mill to obtain carbon powder with the particle size of 3-8 mu M; then mixing the mixture with petroleum asphalt with a softening point of 200 ℃ and xylene according to a mass ratio of 80: 20: 50, adding the mixture into a reaction kettle for coating treatment, wherein the treatment temperature is 220 ℃, and the treatment time is 2 hours; and (3) carbonizing the coated carbon powder in an argon atmosphere at 1100 ℃ for 2h, cooling to room temperature, crushing and sieving to obtain the cathode material with a core-shell structure, wherein the particle size of a core is 3-8 mu m, the thickness of a shell is 100-500nm, and the distance of 002 crystal planes is 0.35 nm. The cell was prepared and the properties are shown in table 1.
Example 2
Drying 1kg of coconut shell in a vacuum drying oven at 110 ℃ for 8h, crushing by a crusher, and carrying out pre-carbonization treatment under argon atmosphere, wherein the heat treatment temperature is 800 ℃ and the time is 2 h; then putting the carbon powder into 1M NaOH solution for ultrasonic cleaning for 2h, then putting the carbon powder into 2M hydrochloric acid solution for ultrasonic cleaning for 2h, washing the carbon powder with deionized water after filtering until the pH value is 7, drying the carbon powder at 110 ℃, and then crushing the carbon powder by using a jet mill to obtain carbon powder with the particle size of 3-8 mu M; adding 100g of carbon powder into N-methyl pyrrolidone for soaking for 5h, heating 25g of petroleum asphalt with the softening point of 200 ℃ to 220 ℃, adding 50ml of N-methyl pyrrolidone, stirring to prepare a mixed solution, adding carbon powder adsorbed with N-methyl pyrrolidone into the asphalt solution while stirring, drying, carbonizing at 1100 ℃ in an argon atmosphere for 2h, cooling to room temperature, crushing and sieving to obtain the cathode material with a core-shell structure, wherein the particle size of a core is 3-8 mu m, the distance between 002 crystal planes is 0.38nm, the thickness of a shell is 100-500nm, and the distance between 002 crystal planes is 0.35 nm. The negative electrode material was made into a button cell, and its performance was shown in table 1.
Example 3
Drying 1kg of coconut shell in a vacuum drying oven at 110 ℃ for 8h, crushing by a crusher, and carrying out pre-carbonization treatment under argon atmosphere, wherein the heat treatment temperature is 500 ℃ and the time is 2 h; then putting the carbon powder into 1M NaOH solution for ultrasonic cleaning for 2h, then putting the carbon powder into 2M hydrochloric acid solution for ultrasonic cleaning for 2h, washing the carbon powder with deionized water after filtering until the pH value is 7, drying the carbon powder at 110 ℃, and then crushing the carbon powder by using a jet mill to obtain carbon powder with the particle size of 3-8 mu M; adding 100g of carbon powder into N-methyl pyrrolidone for soaking for 5h, heating 25g of petroleum asphalt with a softening point of 200 ℃ to 220 ℃, adding 50ml of N-methyl pyrrolidone, stirring to prepare a mixed solution, adding carbon powder adsorbed with N-methyl pyrrolidone into the asphalt solution while stirring, drying, carbonizing at 1200 ℃ for 2h in an argon atmosphere, cooling to room temperature, crushing and sieving to obtain the cathode material with a core-shell structure, wherein the particle size of a core is 3-8 mu m, the spacing between 002 crystal planes is 0.376nm, the thickness of a shell is 100-500nm, and the spacing between 002 crystal planes is 0.35 nm. The negative electrode material was made into button cells, and the properties thereof are shown in table 1.
Example 4
Drying 1kg of coconut shell in a vacuum drying oven at 110 ℃ for 8h, crushing by a crusher, and carrying out pre-carbonization treatment under argon atmosphere, wherein the heat treatment temperature is 500 ℃ and the time is 2 h; then putting the carbon powder into 1M NaOH solution for ultrasonic cleaning for 2h, then putting the carbon powder into 2M hydrochloric acid solution for ultrasonic cleaning for 2h, washing the carbon powder with deionized water after filtering until the pH value is 7, drying the carbon powder at 110 ℃, and then crushing the carbon powder by using a jet mill to obtain carbon powder with the particle size of 3-8 mu M; adding 100g of carbon powder into N-methyl pyrrolidone for soaking for 5h, heating 25g of petroleum asphalt with a softening point of 200 ℃ to 220 ℃, adding 150ml of N-methyl pyrrolidone, stirring to prepare a mixed solution, adding carbon powder adsorbed with N-methyl pyrrolidone into the asphalt solution while stirring, drying, carbonizing at 1300 ℃ for 2h in an argon atmosphere, cooling to room temperature, crushing and sieving to obtain the cathode material with a core-shell structure, wherein the particle size of a core is 3-8 mu m, the spacing between 002 crystal planes is 0.372nm, the thickness of a shell is 100-500nm, and the spacing between 002 crystal planes is 0.35 nm. . The negative electrode material was made into a button cell, and its performance was shown in table 1.
Example 5
Drying 1kg of apricot shells in a vacuum drying oven at 110 ℃ for 8h, crushing the apricot shells by a crusher, and carrying out pre-carbonization treatment in argon atmosphere, wherein the heat treatment temperature is 500 ℃ and the time is 2 h; then putting the carbon powder into 1M NaOH solution for ultrasonic cleaning for 2h, then putting the carbon powder into 2M hydrochloric acid solution for ultrasonic cleaning for 2h, washing the carbon powder with deionized water after filtering until the pH value is 7, drying the carbon powder at 110 ℃, and then crushing the carbon powder by using a jet mill to obtain carbon powder with the particle size of 3-8 mu M; 100g of carbon powder is taken to be added into dimethylacetamide to be soaked for 5h, 25g of petroleum asphalt with the softening point of 200 ℃ is heated to 220 ℃, 150ml of dimethylacetamide is added to be stirred to prepare a mixed solution, carbon powder absorbed with N-methyl pyrrolidone is added into the asphalt solution while stirring, carbonization treatment is carried out for 2h at 1100 ℃ in argon atmosphere after drying, crushing and sieving are carried out after cooling to room temperature, and the cathode material with the core-shell structure is obtained, wherein the particle size of a core is 3-8 mu m, the distance between 002 crystal face layers is 0.38nm, the thickness of a shell is 100-500nm, and the distance between 002 crystal face layers is 0.35 nm. The negative electrode material was made into button cells, and the properties thereof are shown in table 1.
Example 6
Drying 1kg of walnut shells in a vacuum drying oven at 110 ℃ for 8h, crushing by a crusher, and carrying out pre-carbonization treatment under argon atmosphere, wherein the heat treatment temperature is 500 ℃ and the time is 2 h; then putting the carbon powder into 1M NaOH solution for ultrasonic cleaning for 2h, then putting the carbon powder into 2M hydrochloric acid solution for ultrasonic cleaning for 2h, washing the carbon powder with deionized water after filtering until the pH value is 7, drying the carbon powder at 110 ℃, and then crushing the carbon powder by using a jet mill to obtain carbon powder with the particle size of 3-8 mu M; 100g of carbon powder is taken to be added into dimethylacetamide to be soaked for 5h, 25g of petroleum asphalt with the softening point of 200 ℃ is heated to 220 ℃, 150ml of dimethylacetamide is added to be stirred to prepare a mixed solution, carbon powder absorbed with N-methyl pyrrolidone is added into the asphalt solution while stirring, carbonization treatment is carried out for 2h at 1100 ℃ in argon atmosphere after drying, crushing and sieving are carried out after cooling to room temperature, and the cathode material with the core-shell structure is obtained, wherein the particle size of a core is 3-8 mu m, the distance between 002 crystal face layers is 0.38nm, the thickness of a shell is 100-500nm, and the distance between 002 crystal face layers is 0.35 nm. The negative electrode material was made into button cells, and the properties thereof are shown in table 1.
Table 1 battery performance of negative electrode materials prepared in each example and comparative example
The results show that: compared with comparative examples 1 and 2, the first-cycle coulombic efficiency of the battery using the negative electrode material of example 1 of the present invention was increased by 29.8%, and the reversible capacity at rate capability of 5C/the reversible capacity at 0.1C was increased by 9.4%. The charge-discharge reversible capacity was improved by 56.6% as compared with comparative example 3. Compared with comparative example 4, due to the improvement of the coating method, a compact high-order carbon layer can be coated on the surface of the hard carbon particles on the premise of not influencing the internal micropore structure of the hard carbon particles, so that the charge-discharge reversible capacity of the battery is improved by 30.4%, and the first cycle coulombic efficiency is improved by 15.6%. In conclusion, the negative electrode material of the present invention can achieve high first cycle coulombic efficiency while achieving high reversible capacity.
Claims (10)
1. A lithium ion battery negative electrode material is characterized in that:
the material is a carbon material and has a core-shell structure, the particle size of a core is 3-8 mu m, and the interlayer spacing of 002 crystal planes is 0.37-0.41 nm;
the thickness of the shell is 10-1000nm, and the interlayer spacing of 002 crystal planes is 0.34-0.36 nm.
2. The negative electrode material according to claim 1, characterized in that: the battery cathode material is particles with micron-scale particle size formed by tightly combining an inner core shell material and an outer core shell material, and the shell layer material is attached to the outer surface of the core.
3. A method for preparing the anode material according to claim 1 or 2, characterized in that: the preparation method of the cathode material comprises the following steps,
1) drying and crushing a biomass raw material, and then carrying out pre-carbonization treatment for 1-3h at 500-800 ℃ in an inert atmosphere to obtain a product A;
2) sequentially putting the product A into NaOH solution and acid solution, soaking, stirring and cleaning (the cleaning aims at removing impurities except carbon in the raw material (the impurities comprise silicon, metal elements and the like)), then filtering, washing to be neutral, drying, and crushing by a jet mill to obtain carbon powder B with the particle size of 3-8 mu m;
3) and (2) carrying out asphalt coating treatment on the carbon powder B, and specifically comprising the steps of soaking the carbon powder B in a solvent, taking out the carbon powder adsorbed with the solvent, heating the asphalt to 210-350 ℃, adding the solvent, stirring to prepare a mixed solution, adding the carbon powder adsorbed with the solvent into the asphalt solution while stirring, drying, and carrying out carbonization treatment at 1100-1300 ℃ for 1-3h in an inert atmosphere to obtain the cathode material.
4. The method according to claim 3, wherein: the biomass raw material is one or more than two of coconut shell, peach shell, apricot shell and walnut shell.
5. The method according to claim 3, wherein:
the inert atmosphere in the steps 1) and 3) is nitrogen atmosphere and/or argon atmosphere respectively;
the concentration of the NaOH solution in the step 2) is 1-5mol/L, and the acid solution is a hydrochloric acid solution, a sulfuric acid solution or a nitric acid solution, and the concentration is 1-5 mol/L; the dipping and stirring time is 1-100h, preferably 25-50 h; the temperature range during stirring is 25-70 ℃, preferably 50-70 ℃.
6. The method according to claim 3, wherein: the asphalt is petroleum asphalt with a softening point of 200-250 ℃, the asphalt is heated to a temperature 10-50 ℃ higher than the softening point of the asphalt, a solvent is added, and the mixture is stirred to prepare a mixed solution, wherein the mass fraction of the asphalt solution is 30-50%.
7. The method according to claim 3, wherein: the solvent is one or more than two of N-methyl pyrrolidone, dimethyl acetamide, hexamethyl phosphoramidite, hexa ethyl phosphoramidite and diphenyl ether.
8. The method according to claim 3, wherein: the mass ratio of the carbon powder B to the asphalt is 6/4-8/2.
9. A lithium ion battery negative electrode, characterized in that: the active material of the negative electrode is the negative electrode material according to claim 1 or 2.
10. A lithium ion battery, characterized by: the negative electrode of the lithium ion battery is the negative electrode according to claim 9.
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| CN115159503A (en) * | 2022-08-19 | 2022-10-11 | 中国科学技术大学 | Preparation method and application of carbon material with adjustable degree of order |
| CN117623278A (en) * | 2024-01-26 | 2024-03-01 | 碳一新能源(杭州)有限责任公司 | Soft-hard carbon composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106299277A (en) * | 2016-08-30 | 2017-01-04 | 浙江超威创元实业有限公司 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
| CN109599546A (en) * | 2018-12-05 | 2019-04-09 | 中南大学 | Asphalt carbon-coated natural mixed graphite material and method for preparing lithium ion battery cathode by using same |
| CN110148734A (en) * | 2019-05-30 | 2019-08-20 | 蜂巢能源科技有限公司 | Hard carbon cathode material and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106299277A (en) * | 2016-08-30 | 2017-01-04 | 浙江超威创元实业有限公司 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
| CN109599546A (en) * | 2018-12-05 | 2019-04-09 | 中南大学 | Asphalt carbon-coated natural mixed graphite material and method for preparing lithium ion battery cathode by using same |
| CN110148734A (en) * | 2019-05-30 | 2019-08-20 | 蜂巢能源科技有限公司 | Hard carbon cathode material and its preparation method and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115159503A (en) * | 2022-08-19 | 2022-10-11 | 中国科学技术大学 | Preparation method and application of carbon material with adjustable degree of order |
| CN117623278A (en) * | 2024-01-26 | 2024-03-01 | 碳一新能源(杭州)有限责任公司 | Soft-hard carbon composite material and preparation method and application thereof |
| CN117623278B (en) * | 2024-01-26 | 2024-05-07 | 碳一新能源(杭州)有限责任公司 | Soft-hard carbon composite material and preparation method and application thereof |
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