CN108615888B - Biomass carbon fiber negative electrode material for lithium ion battery and preparation method and application thereof - Google Patents
Biomass carbon fiber negative electrode material for lithium ion battery and preparation method and application thereof Download PDFInfo
- Publication number
- CN108615888B CN108615888B CN201810320786.3A CN201810320786A CN108615888B CN 108615888 B CN108615888 B CN 108615888B CN 201810320786 A CN201810320786 A CN 201810320786A CN 108615888 B CN108615888 B CN 108615888B
- Authority
- CN
- China
- Prior art keywords
- negative electrode
- lithium ion
- ion battery
- carbon fiber
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002028 Biomass Substances 0.000 title claims abstract description 115
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 91
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 79
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 75
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 238000001914 filtration Methods 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000003763 carbonization Methods 0.000 claims abstract description 20
- 238000000197 pyrolysis Methods 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000010406 cathode material Substances 0.000 claims abstract description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 23
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 22
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 22
- 241001330002 Bambuseae Species 0.000 claims description 22
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 22
- 239000011425 bamboo Substances 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000007873 sieving Methods 0.000 claims description 14
- 229920002488 Hemicellulose Polymers 0.000 claims description 7
- 229920005610 lignin Polymers 0.000 claims description 7
- 239000001814 pectin Substances 0.000 claims description 7
- 229920001277 pectin Polymers 0.000 claims description 7
- 235000010987 pectin Nutrition 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- -1 stirring Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 239000000835 fiber Substances 0.000 description 16
- 239000003610 charcoal Substances 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 239000010439 graphite Substances 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 244000302661 Phyllostachys pubescens Species 0.000 description 9
- 235000003570 Phyllostachys pubescens Nutrition 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001027 hydrothermal synthesis Methods 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 244000205754 Colocasia esculenta Species 0.000 description 1
- 235000006481 Colocasia esculenta Nutrition 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010796 biological waste Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
Images
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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
-
- 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
- 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
Abstract
The invention discloses a biomass carbon fiber negative electrode material for a lithium ion battery, and a preparation method and application thereof, wherein the biomass carbon fiber negative electrode material for the lithium ion battery is fibrous in microscopic appearance, and the diameter of biomass carbon fiber is 1-5 mu m. The preparation method comprises (1) immersing the biomass raw material in an alkali solution for hydrothermal pretreatment at 120-180 ℃ to obtain a suspension; (2) and filtering the obtained suspension to obtain a precursor, performing ultrasonic dispersion on the precursor, filtering and drying, and heating to 700-1100 ℃ under the protection of inert gas for pyrolysis and carbonization to obtain the cathode material. The negative electrode material disclosed by the invention well keeps fibrous morphology, has the advantages of high first coulombic efficiency, large specific capacity, rich raw material sources of the preparation method, environmental friendliness, reproducibility and simple process, and can be widely applied to the field of lithium ion battery preparation.
Description
Technical Field
The invention mainly relates to the field of lithium ion battery materials, in particular to a biomass carbon fiber negative electrode material for a lithium ion battery and a preparation method thereof.
Background
In recent years, the demand for energy storage systems has been increasing due to the rapid development of portable electronic products such as mobile phones, tablet computers, and notebook computers, and the increasing popularity of new energy electric vehicles. Lithium ion batteries are listed in the compendium for long-term scientific and technical development in China (2006 + 2020) as one of the power sources of new energy automobiles. Graphite is widely used as a negative electrode material of a lithium ion battery because of its advantages of good stability, long cycle life and the like. However, since the theoretical specific capacity of graphite is only 372mAh/g, the graphite anode material has not been able to meet the increasing demand for high energy density and power density. In addition, most graphite cathode materials are prepared by processing natural minerals, and the rapid development of electric automobiles can cause excessive exploitation of graphite mineral resources, so that graphite also faces a dilemma similar to non-renewable resources such as petroleum. In the long term development, as a lithium ion battery for a large-scale commercial electric automobile, an environment-friendly renewable, low-cost and excellent-performance negative electrode material should be adopted.
Biomass-derived carbon materials are receiving increasing attention as an environmentally friendly renewable material. The biomass charcoal material can be prepared by pyrolyzing a plurality of cheap natural raw materials, the microstructure is formed by disordered stacking of graphite sheets, the average interlayer spacing is larger than that of graphite, and the structure of the biomass charcoal material contains a certain number of micropores. Researchers try to directly pyrolyze the biomass raw material to obtain the carbon negative electrode material, however, the carbon negative electrode material has irregular shape and is difficult to completely exert the characteristics of large specific capacity, excellent rate capability and the like when being applied to the negative electrode material. For example, chinese patent publication No. CN107623105A discloses that a carbon negative electrode material prepared from biological waste (such as taro stem, rice hull, etc.) has disadvantages of long preparation time, complicated steps, etc., which results in high cost and difficult commercialization, and the carbon material has large particle size and irregular morphology, and is difficult to exert the advantages of biomass carbon material. The chinese patent publication No. CN106948032A discloses that commercial cellulose is used as a raw material, and a carbon fiber negative electrode material is prepared through catalytic graphitization, and the carbon fiber negative electrode material prepared by the method has the characteristics of unobvious fibrous morphology, small specific capacity (368mAh/g) and the like, and is difficult to truly replace the existing graphite negative electrode material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a biomass carbon fiber negative electrode material for a lithium ion battery, which can efficiently reserve fibrous morphology, has high first coulombic efficiency and large specific capacity, and also provides a preparation method of the biomass carbon fiber negative electrode material for the lithium ion battery, which has rich raw material sources, is environment-friendly and renewable, has a simple process flow, and particularly can efficiently reserve the fibrous morphology, and correspondingly provides application of the biomass carbon fiber negative electrode material.
The biomass carbon fiber negative electrode material for the lithium ion battery is fibrous in microscopic appearance, the diameter of biomass carbon fiber is 1-5 mu m, the first discharge specific capacity of the biomass carbon fiber negative electrode material for the lithium ion battery is 410-770 mAh/g under the condition that the charge and discharge current is 50mA/g, and the first coulombic efficiency is 65-85%.
As a general technical concept, the invention also provides a preparation method of the biomass carbon fiber negative electrode material for the lithium ion battery, which comprises the following steps:
(1) immersing a biomass raw material into an alkali solution, and carrying out hydrothermal pretreatment at 120-180 ℃ to remove lignin, hemicellulose and pectin components in the biomass raw material to obtain a suspension;
(2) and (2) filtering the suspension obtained in the step (1) to obtain a precursor, performing ultrasonic dispersion on the precursor in water, filtering and drying, heating the dried precursor to 700-1100 ℃ under the protection of inert gas for pyrolysis and carbonization, and cooling to room temperature to obtain the biomass carbon fiber cathode material for the lithium ion battery.
In the above preparation method of the biomass charcoal fiber negative electrode material for the lithium ion battery, preferably, in the step (1), the biomass raw material includes wood and/or bamboo, and the alkali solution includes one or more of LiOH aqueous solution, NaOH aqueous solution and KOH aqueous solution;
and/or the ratio of the mass of the biomass raw material to the volume of the alkali solution is 3 g-10 g: 40 mL-70 mL, and the concentration of the alkali solution is 1 mol/L-5 mol/L.
In the above preparation method of the biomass charcoal fiber negative electrode material for the lithium ion battery, preferably, in the step (1), the biomass raw material is crushed and sieved before being immersed in the alkali solution, and the sieving is performed by 40-100 mesh sieving.
In the above preparation method of the biomass charcoal fiber negative electrode material for the lithium ion battery, preferably, in the step (1), the hydrothermal pretreatment time is 2 to 8 hours.
In the preparation method of the biomass carbon fiber negative electrode material for the lithium ion battery, preferably, in the step (2), the temperature rise rate is 1 ℃/min to 10 ℃/min, and the pyrolysis carbonization time is 1h to 3 h.
In the above preparation method of the biomass charcoal fiber negative electrode material for the lithium ion battery, preferably, in the step (2), the ultrasonic dispersion time is 10min to 120 min.
In the above preparation method of the biomass charcoal fiber negative electrode material for the lithium ion battery, preferably, in the step (2), after cooling to room temperature, a grinding step is further included, and the grinding time is 10min to 30 min.
As a general technical concept, the invention also provides an application of the biomass carbon fiber negative electrode material for the lithium ion battery or the biomass carbon fiber negative electrode material for the lithium ion battery prepared by the preparation method in the preparation of the lithium ion battery.
In the above application, preferably, the application comprises the following steps: mixing a biomass carbon fiber negative electrode material for a lithium ion battery, conductive carbon black and a binder, adding the obtained mixture into an N-methyl pyrrolidone solvent, stirring, coating a film on a copper foil to prepare a negative electrode plate, taking a metal lithium plate as a counter electrode, and taking LiPF6The EC/DMC/EMC mixed solution is taken as electrolyte, a Celgard2400 polypropylene film is taken as a diaphragm, and the button cell is assembled, so that the lithium ion battery is obtained.
In the step (1) of the production method of the present invention, deionized water is usually used as the water to be hydrothermally pretreated.
The main innovation points of the invention are as follows:
1. the applicant finds through long-term experimental research that in the prior art, biomass raw materials are usually directly pyrolyzed into biomass charcoal materials and then applied to the field of negative electrode materials, however, the first specific capacity and the coulombic efficiency of the biomass charcoal materials prepared in the way are general, and the applicant finds that the morphology of the biomass charcoal materials plays an important role in the first specific capacity and the coulombic efficiency, so that the applicant carries out deep research and development on the technical problem.
2. According to the technical scheme, before the biomass raw material is pyrolyzed, hydrothermal pretreatment is performed, the hydrothermal pretreatment is mainly used for removing components such as lignin, hemicellulose and pectin in the biomass raw material to obtain a primary fiber bundle precursor, and then pyrolysis is performed on the basis, so that the morphology of a large number of primary fiber bundles can be kept, the first discharge specific capacity and the first coulombic efficiency of the obtained biomass carbon fiber negative electrode material are obviously improved, and the biomass carbon fiber negative electrode material has outstanding advantages compared with the prior art.
Compared with the prior art, the invention has the advantages that:
(1) the biomass carbon fiber negative electrode material for the lithium ion battery has the advantages that the microscopic morphology is fibrous, the natural fibrous morphology in a biomass raw material can be reserved, the diameter is 1-5 mu m, the charge-discharge specific capacity (such as 570mAh/g) is larger than that of graphite (372mAh/g), the biomass carbon fiber negative electrode material for the lithium ion battery has unique anisotropy, rapid axial electron transmission and radial ion diffusion characteristics, when the biomass carbon fiber negative electrode material is used as an electrode active material, the lithium ion migration path is greatly shortened, lithium ions can rapidly shuttle among the lithium ion migration paths, the rate capability of the lithium ion battery is improved, the primary efficiency is higher, the specific capacity is large, and the large-current charge-discharge performance and the cycling stability are good.
(2) The preparation method of the biomass carbon fiber cathode material for the lithium ion battery can eliminate the agglomeration phenomenon of carbon fibers after pyrolysis and carbonization in biomass raw materials, is convenient for post-treatment of the materials, removes pectin, hemicellulose and lignin in the biomass raw materials due to the fact that the biomass raw materials are rich in cellulose and have developed fiber structures to obtain a primary fiber bundle precursor, and can obtain the biomass carbon fiber cathode material for the lithium ion battery with the diameter of micron after high-temperature carbonization.
Drawings
Fig. 1 is a scanning electron microscope image of the biomass charcoal fiber negative electrode material for the lithium ion battery in example 1 of the present invention under different magnifications, wherein the magnification of fig. a is 600, and the magnification of fig. b is 5000.
Fig. 2 is a first charge-discharge curve diagram of the biomass charcoal fiber negative electrode material for the lithium ion battery in example 1 of the present invention.
Fig. 3 is a first charge-discharge curve diagram of the biomass charcoal fiber negative electrode material for the lithium ion battery in example 2 of the present invention.
Fig. 4 is a first charge-discharge curve diagram of the biomass charcoal fiber negative electrode material for the lithium ion battery in example 3 of the present invention.
FIG. 5 is a Scanning Electron Microscope (SEM) image of the carbon material in comparative example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available.
The biomass carbon fiber negative electrode material for the lithium ion battery is fibrous in microscopic appearance and has the diameter of 1-5 microns. The biomass carbon fiber negative electrode material for the lithium ion battery has the first discharge specific capacity of 410 mAh/g-770 mAh/g and the first coulombic efficiency of 65-85% under the condition that the charge-discharge current is 50 mA/g.
A preparation method of a biomass carbon fiber negative electrode material for a lithium ion battery comprises the following steps:
(1) immersing a biomass raw material into an alkali solution, and carrying out hydrothermal pretreatment at 120-180 ℃ to remove lignin, hemicellulose and pectin components in the biomass raw material to obtain a suspension;
(2) and (2) filtering the suspension obtained in the step (1) to obtain a precursor, performing ultrasonic dispersion on the precursor in water, filtering and drying, heating the dried precursor to 700-1100 ℃ under the protection of inert gas for pyrolysis and carbonization, and cooling to room temperature to obtain the biomass carbon fiber cathode material for the lithium ion battery.
In the step (1), preferably, the biomass raw material includes wood and/or bamboo, and the alkali solution includes one or more of LiOH aqueous solution, NaOH aqueous solution and KOH aqueous solution; the ratio of the mass of the biomass raw material to the volume of the alkali solution is 3 g-10 g: 40 mL-70 mL, and the concentration of the alkali solution is 1 mol/L-5 mol/L. The biomass raw material is crushed and sieved before being immersed in the alkali solution, wherein the sieving is 40-100-mesh sieving. The time of the hydrothermal pretreatment is 2-8 h, and the water of the hydrothermal pretreatment is deionized water.
In the step (2), preferably, the temperature rising rate is 1 ℃/min to 10 ℃/min, and the pyrolysis carbonization time is 1h to 3 h. The time of ultrasonic dispersion is 10 min-120 min. And after cooling to room temperature, further comprising a grinding step, wherein the grinding time is 10-30 min.
The preparation method can eliminate the agglomeration phenomenon of the carbon fiber after the biomass raw material is pyrolyzed and carbonized, is convenient for the post-treatment of the material, has a developed fiber structure due to the fact that the biomass raw material is rich in cellulose, removes pectin, hemicellulose and lignin in the biomass raw material to obtain a primary fiber bundle precursor, and can obtain the biomass carbon fiber cathode material for the lithium ion battery with the diameter of micron after high-temperature carbonization.
Example 1:
the invention relates to a biomass carbon fiber negative electrode material for a lithium ion battery, which is fibrous in microscopic appearance, and the diameter of biomass carbon fiber is 1-5 mu m. When the charging and discharging current is 50mA/g, the first discharging specific capacity reaches 766.7mAh/g, and the first coulombic efficiency is 69.0%.
The preparation method of the biomass carbon fiber negative electrode material for the lithium ion battery comprises the following steps:
(1) removing bamboo green of moso bamboo, crushing and sieving with a 40-mesh sieve, weighing 5g of bamboo powder, adding into 70mL of NaOH aqueous solution with the concentration of 3mol/L, soaking completely, transferring into a 100mL hydrothermal reaction kettle for hydrothermal pretreatment, heating to 140 ℃, and preserving heat for 6h to remove components such as lignin, hemicellulose, pectin and the like. After the reaction is finished, cooling to room temperature to obtain a suspension.
(2) And filtering the obtained suspension to obtain a precursor, performing ultrasonic dispersion on the precursor in water for 30min, filtering and drying, putting the dried precursor into a tubular furnace filled with argon for pyrolysis and carbonization, heating to 1000 ℃ at a speed of 10 ℃/min, and preserving heat for 1 h. And after pyrolysis and carbonization, cooling to room temperature, and grinding for 10min to obtain the biomass carbon fiber negative electrode material powder for the lithium ion battery.
The scanning electron microscope image of the biomass carbon fiber negative electrode material for the lithium ion battery prepared in the embodiment is shown in fig. 1, and it can be seen that the micro-morphology of the negative electrode material is fibrous, the diameter is in the range of 1 μm to 5 μm, the average diameter is about 3 μm, and the size distribution is relatively uniform.
An application of the biomass carbon fiber negative electrode material for the lithium ion battery prepared in the embodiment includes the following steps:
mixing 0.32g of the biomass carbon fiber negative electrode material powder for the lithium ion battery prepared in the embodiment with conductive carbon black and a binder (PVDF), wherein the mass ratio of the biomass carbon fiber negative electrode material to the conductive carbon black to the binder is 8: 1, adding the obtained mixture into an N-methylpyrrolidone solvent, stirring for 6 hours, and then coating on a copper foil to prepare a negative electrode plate; then using a metal lithium sheet as a counter electrode and LiPF6The EC/DMC/EMC (i.e. ethylene carbonate/dimethyl carbonate/ethyl methyl carbonate) mixed solution is used as electrolyte, and LiPF is added into the electrolyte6The concentration of the monomer is 1mol/L, the mass ratio of EC to DMC to EMC is 1: 1, and a Celgard2400 polypropylene film is taken as a diaphragm to assemble the button cell. The first discharge specific capacity of the biomass carbon fiber negative electrode material for the lithium ion battery of the embodiment reaches 766.7mAh/g and the first coulombic efficiency reaches 69.0% when the charge and discharge current is 50 mA/g. The first charge-discharge curve is shown in fig. 2, and it can be seen that the voltage hysteresis effect between the charge curve and the discharge curve is small, and the requirements of the lithium ion battery on high voltage and high energy density can be met.
Example 2:
the invention discloses a preparation method of a biomass carbon fiber negative electrode material for a lithium ion battery, which comprises the following steps:
(1) removing bamboo green of moso bamboo, crushing, sieving with a 40-mesh sieve, weighing 5g of bamboo powder, adding into 70mL of NaOH aqueous solution with the concentration of 3mol/L, soaking completely, transferring into a 100mL hydrothermal reaction kettle for hydrothermal pretreatment, heating to 150 ℃, and preserving heat for 6 h. After the reaction is finished, cooling to room temperature to obtain a suspension.
(2) And filtering the obtained suspension to obtain a precursor, and then ultrasonically dispersing the precursor in water for 30min, filtering and drying. And putting the dried precursor into a tubular furnace filled with argon for pyrolysis and carbonization, heating to 1000 ℃ at a speed of 10 ℃/min, and preserving heat for 1 h. And cooling to room temperature, and grinding for 10min to obtain the powdery biomass carbon fiber negative electrode material for the lithium ion battery, wherein the microscopic morphology of the biomass carbon fiber negative electrode material is fibrous.
The button battery is assembled according to the application scheme in the example 1, and the first specific discharge capacity of the negative electrode material prepared in the example reaches 555.1mAh/g under the condition that the charge and discharge current is 50mA/g, and the first coulombic efficiency is 73.7 percent. The first charge-discharge curve is shown in fig. 3, and it can be seen that the voltage hysteresis effect between the charge curve and the discharge curve is small, and the requirements of the lithium ion battery on high voltage and high energy density can be met.
Example 3:
the invention discloses a preparation method of a biomass carbon fiber negative electrode material for a lithium ion battery, which comprises the following steps:
(1) removing bamboo green of moso bamboo, crushing, sieving with a 40-mesh sieve, weighing 5g of bamboo powder, adding into 70mL of NaOH aqueous solution with the concentration of 3mol/L, soaking completely, transferring into a 100mL hydrothermal reaction kettle for hydrothermal pretreatment, heating to 150 ℃, and preserving heat for 6 h. After the reaction is finished, cooling to room temperature to obtain a suspension.
(2) And filtering the obtained suspension to obtain a precursor, and then ultrasonically dispersing the precursor in water for 30min, filtering and drying. And putting the dried precursor into a tube furnace filled with argon for pyrolysis and carbonization, heating to 1100 ℃ at the speed of 10 ℃/min, and preserving heat for 1 h. And cooling to room temperature, and grinding for 10min to obtain the biomass carbon fiber negative electrode material for the lithium ion battery, wherein the microscopic morphology of the biomass carbon fiber negative electrode material is fibrous.
The button cell is assembled according to the application method of the embodiment 1, and the first specific discharge capacity of the negative electrode material prepared in the embodiment reaches 439.4mAh/g under the condition that the charge and discharge current is 50mA/g, and the first coulombic efficiency is 84.6 percent. The first charge-discharge curve is shown in fig. 4, and it can be seen that the voltage hysteresis effect between the charge curve and the discharge curve is small, and the requirements of the lithium ion battery on high voltage and high energy density can be met.
Example 4:
the invention discloses a preparation method of a biomass carbon fiber negative electrode material for a lithium ion battery, which comprises the following steps:
(1) removing bamboo green from Phyllostachys Pubescens, pulverizing, sieving with 40 mesh sieve, weighing 5g bamboo powder, and adding into 70mL NaOH aqueous solution with concentration of 3 mol/L; and transferring the soaked mixture into a 100mL hydrothermal reaction kettle for hydrothermal pretreatment, heating to 150 ℃, and preserving heat for 6 hours. After the reaction is finished, cooling to room temperature to obtain a suspension.
(2) And filtering the obtained suspension to obtain a precursor, and then ultrasonically dispersing the precursor in water for 30min, filtering and drying. And putting the dried precursor into a tubular furnace filled with argon for pyrolysis and carbonization, heating to 900 ℃ at a speed of 10 ℃/min, and preserving heat for 1 h. And cooling to room temperature, and grinding for 10min to obtain the biomass carbon fiber negative electrode material for the lithium ion battery, wherein the microscopic morphology of the biomass carbon fiber negative electrode material is fibrous.
The button cell is assembled by the application method of the embodiment 1, and the first specific discharge capacity of the prepared negative electrode material under the condition of the charge and discharge current of 50mA/g is 615.2mAh/g, and the first coulombic efficiency is 66.2 percent.
Example 5:
the invention discloses a preparation method of a biomass carbon fiber negative electrode material for a lithium ion battery, which comprises the following steps:
(1) removing bamboo green from Phyllostachys Pubescens, pulverizing, sieving with 40 mesh sieve, weighing 5g bamboo powder, and adding into 70mL NaOH aqueous solution with concentration of 3 mol/L; and transferring the soaked mixture into a 100mL hydrothermal reaction kettle for hydrothermal pretreatment, heating to 150 ℃, and preserving heat for 2 hours. After the reaction is finished, cooling to room temperature to obtain a suspension.
(2) And filtering the obtained suspension to obtain a precursor, and then ultrasonically dispersing the precursor in water for 60min, filtering and drying. And putting the dried precursor into a tubular furnace filled with argon for pyrolysis and carbonization, heating to 1000 ℃ at a speed of 10 ℃/min, and preserving heat for 1 h. And cooling to room temperature, and grinding for 10min to obtain the biomass carbon fiber negative electrode material for the lithium ion battery, wherein the microscopic morphology of the biomass carbon fiber negative electrode material is fibrous.
The button cell is assembled by the application method of the embodiment 1, and the first specific discharge capacity of the negative electrode material prepared in the embodiment is 470.3.4mAh/g under the condition that the charge and discharge current is 50mA/g, and the first coulombic efficiency is 80.8 percent.
Example 6:
the invention discloses a preparation method of a biomass carbon fiber negative electrode material for a lithium ion battery, which comprises the following steps:
(1) removing bamboo green of moso bamboo, crushing, sieving with a 40-mesh sieve, weighing 5g of bamboo powder, adding into 70mL of NaOH aqueous solution with the concentration of 3mol/L, soaking completely, transferring into a 100mL hydrothermal reaction kettle for hydrothermal pretreatment, heating to 150 ℃, and preserving heat for 8 hours. After the reaction is finished, cooling to room temperature to obtain a suspension.
(2) And filtering the obtained suspension to obtain a precursor, and then ultrasonically dispersing the precursor in water for 15min, filtering and drying. And putting the dried precursor into a tubular furnace filled with argon for pyrolysis and carbonization, heating to 1000 ℃ at a speed of 10 ℃/min, and preserving heat for 1 h. And cooling to room temperature, and grinding for 10min to obtain the biomass carbon fiber negative electrode material for the lithium ion battery, wherein the microscopic morphology of the biomass carbon fiber negative electrode material is fibrous.
The button cell is assembled by the application method of the embodiment 1, and the first specific discharge capacity of the negative electrode material prepared in the embodiment reaches 564.7mAh/g under the condition that the charge and discharge current is 50mA/g, and the first coulombic efficiency is 66.6 percent.
Example 7:
the invention discloses a preparation method of a biomass carbon fiber negative electrode material for a lithium ion battery, which comprises the following steps:
(1) removing bamboo green from moso bamboo, crushing, sieving with a 40-mesh sieve, weighing 5g of bamboo powder, adding into 70mL of 1mol/L NaOH aqueous solution, soaking completely, transferring into a 100mL hydrothermal reaction kettle for hydrothermal pretreatment, heating to 150 ℃, and keeping the temperature for 6 h. After the reaction is finished, cooling to room temperature to obtain a suspension.
(2) And filtering the obtained suspension to obtain a precursor, ultrasonically dispersing the precursor in water for 30min, and filtering and drying. And putting the dried precursor into a tube furnace filled with argon for pyrolysis and carbonization, heating to 1100 ℃ at the speed of 10 ℃/min, and preserving heat for 1 h. And cooling to room temperature, and grinding for 10min to obtain the biomass carbon fiber negative electrode material for the lithium ion battery, wherein the microscopic morphology of the biomass carbon fiber negative electrode material is fibrous.
The button cell is assembled by the application method of the embodiment 1, and the first specific discharge capacity of the negative electrode material prepared in the embodiment is 468.1mAh/g under the condition that the charge and discharge current is 50mA/g, and the first coulombic efficiency is 81.9 percent.
Example 8:
the invention discloses a preparation method of a biomass carbon fiber negative electrode material for a lithium ion battery, which comprises the following steps:
(1) removing bamboo green from Phyllostachys Pubescens, pulverizing, sieving with 40 mesh sieve, weighing 5g bamboo powder, and adding into 70mL NaOH aqueous solution with concentration of 4 mol/L; and transferring the soaked mixture into a 100mL hydrothermal reaction kettle for hydrothermal pretreatment, heating to 150 ℃, and preserving heat for 6 hours. After the reaction is finished, cooling to room temperature to obtain a suspension.
(2) And filtering the obtained suspension to obtain a precursor, ultrasonically dispersing the precursor in water for 30min, and filtering and drying. And putting the dried precursor into a tubular furnace filled with argon for pyrolysis and carbonization, heating to 900 ℃ at a speed of 10 ℃/min, and preserving heat for 3 hours. And cooling to room temperature, and grinding for 10min to obtain the biomass carbon fiber negative electrode material for the lithium ion battery, wherein the microscopic morphology of the biomass carbon fiber negative electrode material is fibrous.
The button cell is assembled by the application method of the embodiment 1, and the first specific discharge capacity of the negative electrode material under the condition of the charge and discharge current of 50mA/g is 695.2mAh/g, and the first coulombic efficiency is 65.9 percent.
Comparative example 1 non-hydrothermal pretreatment
A preparation method of a biomass charcoal negative electrode material for a lithium ion battery comprises the following steps:
removing bamboo green from Phyllostachys Pubescens, pulverizing, sieving with 40 mesh sieve, weighing 5g bamboo powder, putting into a tube furnace filled with argon gas, performing pyrolysis carbonization, heating to 1000 deg.C at 10 deg.C/min, and maintaining the temperature for 1 h. Cooling to room temperature, and grinding for 10min to obtain powdered carbon material. The scanning electron microscope image of the carbon material prepared by the comparative example is shown in fig. 5, and it can be seen that the material is basically composed of blocky particles with irregular shapes and has no obvious fiber shapes.
The button cell is assembled according to the application method of the embodiment 1, and the first specific discharge capacity of the negative electrode material is only 401.8mAh/g under the condition that the charge and discharge current is 50mA/g, the first coulombic efficiency is 69.9 percent, and the specific capacity data of the negative electrode material is lower than that of the carbon fiber negative electrode material obtained in other embodiments.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (5)
1. A preparation method of a biomass carbon fiber negative electrode material for a lithium ion battery comprises the following steps:
(1) immersing a biomass raw material into an alkaline solution, wherein the biomass raw material is wood and/or bamboo, performing hydrothermal pretreatment at 120-180 ℃, and removing lignin, hemicellulose and pectin components in the biomass raw material to obtain a suspension;
(2) filtering the suspension obtained in the step (1) to obtain a precursor, performing ultrasonic dispersion on the precursor in water, filtering and drying, heating the dried precursor to 1000-1100 ℃ under the protection of inert gas for pyrolysis and carbonization, and cooling to room temperature to obtain the biomass carbon fiber cathode material for the lithium ion battery; the micro-morphology of the biomass carbon fiber negative electrode material for the lithium ion battery is fibrous, the diameter of the biomass carbon fiber is 1-5 mu m, the biomass raw material of the biomass carbon fiber is wood and/or bamboo, the first discharge specific capacity of the biomass carbon fiber negative electrode material for the lithium ion battery is 410-770 mAh/g under the condition of the charge and discharge current of 50mA/g, and the first coulombic efficiency is 65-85%;
in the step (1), the alkali solution comprises one or more of a LiOH aqueous solution, a NaOH aqueous solution and a KOH aqueous solution;
the ratio of the mass of the biomass raw material to the volume of the alkali solution is 3 g-10 g: 40 mL-70 mL, and the concentration of the alkali solution is 1 mol/L-5 mol/L;
in the step (1), the biomass raw material is crushed and sieved before being immersed in the alkali solution, and the sieving is 40-100 meshes;
in the step (1), the hydrothermal pretreatment time is 2-8 h;
in the step (2), the heating rate is 1-10 ℃/min, and the pyrolysis carbonization time is 1-3 h.
2. The preparation method of the biomass carbon fiber negative electrode material for the lithium ion battery according to claim 1, wherein in the step (2), the ultrasonic dispersion time is 10min to 120 min.
3. The preparation method of the biomass carbon fiber negative electrode material for the lithium ion battery according to claim 1, wherein in the step (2), after cooling to room temperature, the method further comprises a grinding step, and the grinding time is 10-30 min.
4. Application of the biomass carbon fiber negative electrode material for the lithium ion battery prepared by the preparation method of any one of claims 1 to 3 in preparation of the lithium ion battery.
5. The application according to claim 4, characterized in that it comprises the following steps: mixing a biomass carbon fiber negative electrode material for a lithium ion battery, conductive carbon black and a binder, adding the obtained mixture into an N-methyl pyrrolidone solvent, stirring, coating a film on a copper foil to prepare a negative electrode plate, and taking a metal lithium plate as a negative electrode plateTo the electrode, with LiPF6The EC/DMC/EMC mixed solution is taken as electrolyte, a Celgard2400 polypropylene film is taken as a diaphragm, and the button cell is assembled, so that the lithium ion battery is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810320786.3A CN108615888B (en) | 2018-04-11 | 2018-04-11 | Biomass carbon fiber negative electrode material for lithium ion battery and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810320786.3A CN108615888B (en) | 2018-04-11 | 2018-04-11 | Biomass carbon fiber negative electrode material for lithium ion battery and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108615888A CN108615888A (en) | 2018-10-02 |
| CN108615888B true CN108615888B (en) | 2021-06-22 |
Family
ID=63659620
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810320786.3A Expired - Fee Related CN108615888B (en) | 2018-04-11 | 2018-04-11 | Biomass carbon fiber negative electrode material for lithium ion battery and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108615888B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109768222A (en) * | 2019-01-11 | 2019-05-17 | 五邑大学 | A kind of preparation method based on biomass carbon/cobalt acid nickel needle composite material negative electrode of lithium ion battery |
| CN110467173A (en) * | 2019-07-31 | 2019-11-19 | 桑德新能源技术开发有限公司 | Amorphous carbon material and preparation method thereof, negative electrode material, lithium ion battery |
| CN111211301A (en) * | 2020-01-10 | 2020-05-29 | 上海工程技术大学 | Flexible organic compound/biomass carbon fiber composite material and preparation method thereof |
| CN116216691A (en) * | 2023-02-02 | 2023-06-06 | 湖北万润新能源科技股份有限公司 | Hard carbon and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105552372A (en) * | 2016-01-27 | 2016-05-04 | 太原理工大学 | N-doped carbon micro-fibre material, and preparation method and application thereof |
| CN107623105A (en) * | 2017-10-09 | 2018-01-23 | 江西理工大学 | A kind of preparation method of lithium ion battery GND and conductive agent material |
-
2018
- 2018-04-11 CN CN201810320786.3A patent/CN108615888B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105552372A (en) * | 2016-01-27 | 2016-05-04 | 太原理工大学 | N-doped carbon micro-fibre material, and preparation method and application thereof |
| CN107623105A (en) * | 2017-10-09 | 2018-01-23 | 江西理工大学 | A kind of preparation method of lithium ion battery GND and conductive agent material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108615888A (en) | 2018-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108615888B (en) | Biomass carbon fiber negative electrode material for lithium ion battery and preparation method and application thereof | |
| CN108751160B (en) | Lignin porous carbon with uniform pore channels, preparation method thereof and application thereof in lithium ion battery cathode material | |
| CN108923047B (en) | Hollow carbon fiber negative electrode material for lithium ion battery and preparation method and application thereof | |
| CN105845936A (en) | Preparation method of modified hard carbon negative electrode material for lithium ion battery | |
| CN109755532B (en) | Wood carbon fiber/metal oxide/graphene composite negative electrode material and preparation method and application thereof | |
| CN107946568B (en) | High-performance silicon oxide/hard carbon/graphite composite material and preparation method and application thereof | |
| CN110797533A (en) | Lignin hard carbon microsphere, hydrothermal preparation method and application of lignin hard carbon microsphere in alkali metal ion battery cathode | |
| CN103840161A (en) | Method for preparing lithium battery negative electrode material, and lithium battery negative electrode sheet | |
| CN113044827A (en) | Nano carbon material composite biomass hard carbon electrode material and preparation method and application thereof | |
| CN113889593B (en) | Preparation method of hard carbon-coated soft carbon composite material | |
| CN112408359B (en) | Method for preparing battery negative electrode material by using enzymatic hydrolysis lignin-based epoxy resin | |
| Yan et al. | Hierarchically porous carbon derived from wheat straw for high rate lithium ion battery anodes | |
| CN110190284B (en) | Water-based binder for lithium-sulfur battery positive electrode and preparation method and application thereof | |
| CN112110448A (en) | Nitrogen-doped carbon and nano-silicon composite anode material and preparation method thereof | |
| CN113889594A (en) | Preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material | |
| CN113422009B (en) | Lithium ion battery cathode material and preparation method and application thereof | |
| CN114702022A (en) | Preparation method and application of hard carbon negative electrode material | |
| CN116979064B (en) | Carbon material and preparation method thereof, negative electrode plate, secondary battery and power utilization device | |
| CN103996833A (en) | Modified hard carbon microsphere negative material for lithium ion battery and preparation method of material | |
| CN113548654A (en) | Method for preparing hard carbon material from biomass waste physalis pubescens fruit leaves and sodium ion battery | |
| CN109742367B (en) | Wood carbon fiber/metal oxide composite negative electrode material and preparation method and application thereof | |
| CN111313012A (en) | Multiwalled carbon nanotube graphite lithium ion battery negative electrode material and preparation method thereof | |
| CN108767193B (en) | Positive electrode containing low-swelling graphite coating and lithium battery | |
| Yang et al. | Natural wood-derived free-standing films as efficient and stable separators for high-performance lithium ion batteries | |
| CN113506862B (en) | Nano carbon fiber composite material for lithium-sulfur battery anode and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210622 |