CN114497545A - Hard carbon negative electrode material and preparation method and application thereof - Google Patents
Hard carbon negative electrode material and preparation method and application thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 97
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229920002472 Starch Polymers 0.000 claims abstract description 46
- 239000008107 starch Substances 0.000 claims abstract description 43
- 235000019698 starch Nutrition 0.000 claims abstract description 43
- 239000011148 porous material Substances 0.000 claims abstract description 33
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 45
- 238000004132 cross linking Methods 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000010405 anode material Substances 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 229920002261 Corn starch Polymers 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 11
- 239000008120 corn starch Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 229920000945 Amylopectin Polymers 0.000 claims description 6
- 239000012798 spherical particle Substances 0.000 claims description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 5
- 229920001592 potato starch Polymers 0.000 claims description 5
- 229920000856 Amylose Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229940100445 wheat starch Drugs 0.000 claims description 3
- 244000017020 Ipomoea batatas Species 0.000 claims description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000007363 ring formation reaction Methods 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 abstract description 11
- 239000010406 cathode material Substances 0.000 abstract description 5
- 238000009831 deintercalation Methods 0.000 abstract description 5
- 238000009830 intercalation Methods 0.000 abstract description 4
- 230000002687 intercalation Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 44
- 239000000047 product Substances 0.000 description 26
- 238000005245 sintering Methods 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 18
- 239000003575 carbonaceous material Substances 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- -1 trona Chemical compound 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 241001625808 Trona Species 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Classifications
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- 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 hard carbon cathode material and a preparation method and application thereof. The substrate of the hard carbon negative electrode material is prepared by taking starch as a raw material; the diameter of the internal pores of the hard carbon negative electrode material is larger than the diameter of the surface pores. The reasonable pore diameter and the large interlayer spacing of the hard carbon cathode material are beneficial to the intercalation/deintercalation of sodium ions.
Description
Technical Field
The invention belongs to the technical field of battery cathode materials, and particularly relates to a hard carbon cathode material and a preparation method and application thereof.
Background
With the gradual decrease of traditional fossil energy and the gradual increase of environmental pollution, the development and utilization of energy are important. Lithium ion batteries have become the main energy storage devices in the consumer electronics field with the advantages of high energy density, high voltage, low self-discharge, and excellent cycle performance. However, the lithium resources on the earth are few, and the wide application of the lithium ion battery makes the lithium resources more short, the price is high, and the lithium ion battery is not suitable for large-scale energy storage application, so that the development of the next generation of energy storage battery system with excellent comprehensive performance is urgently needed.
Sodium and lithium belong to the same group elements, and have similar physicochemical properties with lithium, abundant reserves and low price (the basic raw material of sodium, namely trona, is about 30 to 40 times cheaper than the raw material of lithium, namely lithium carbonate), and the electrode potential (Na) of the sodium is higher than that of the lithium+Na) is more lithium-ion (Li)+the/Li) is 0.3V higher, and has more stable electrochemical performance and safety performance. However, the ionic radius (r ═ 0.113nm) of sodium ions is at least 35% greater than that of lithium ions (r ═ 0.076), so that sodium ions are relatively stable in a rigid lattice, are difficult to reversibly deintercalate in a regular graphite structure, and have almost no sodium storage capacity.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows:
a hard carbon anode material is provided. The reasonable pore diameter and the large interlayer spacing of the hard carbon cathode material are beneficial to the intercalation/deintercalation of sodium ions.
The second technical problem to be solved by the invention is:
a preparation method of the hard carbon negative electrode material is provided.
The invention also provides a hard carbon cathode.
In order to solve the first technical problem, the invention adopts the technical scheme that:
a substrate of the hard carbon negative electrode material is prepared by taking starch as a raw material;
the diameter of the internal pores of the hard carbon negative electrode material is larger than the diameter of the surface pores.
According to one embodiment of the invention, the hard carbon anode material interlayer spacing is greater than 0.34 nm.
The ion diameter of the sodium ions is about 0.226nm, that is, the distance between the anode material layers is at least greater than 0.226nm, so that the sodium ions can be theoretically freely inserted into and extracted from the anode material layers, but actually, the alternating layer structure in the anode material affects the conduction of the sodium ions to some extent. When the interlayer spacing of the anode material reaches 0.34nm, sodium ions still have difficulty in realizing free reversible deintercalation, so that the interlayer spacing of the anode material is at least greater than 0.34 nm.
According to one embodiment of the invention, the hard carbon anode material interlayer spacing is about 3.828 nm.
According to one embodiment of the invention, the internal pores have a diameter X, 0 < X.ltoreq.5 nm.
According to one embodiment of the invention, the diameter of the internal pores of the hard carbon negative electrode material is between 0 and 5nm, and the diameter is in the range, so that sodium ions can be embedded and removed, and the hard carbon negative electrode material has sodium storage capacity and cycling stability.
According to one embodiment of the present invention, the internal porosity of the hard carbon anode material is dominated by 2 nm.
According to an embodiment of the present invention, the pore diameter of the surface of the hard carbon negative electrode material is smaller than the internal pore of the hard carbon negative electrode material, and the sodium ions can pass through the external pore of the hard carbon negative electrode material, but since the pore diameter of the surface is very small, a substance larger than ions is difficult to pass through the external pore, and unnecessary impurities are prevented from being doped into the hard carbon negative electrode material, thereby ensuring a good sodium storage environment inside the hard carbon negative electrode material. In addition, a large number of irregular pores exist in the spherical particles, so that the sodium storage capacity in the hard carbon negative electrode material can be further enhanced.
According to one embodiment of the invention, the hard carbon negative electrode material is subjected to a charge-discharge cycle test through a blue test cabinet, so that the average sodium insertion capacity of the hard carbon negative electrode material is 330 mAh/g.
According to one embodiment of the invention, the starch is amylose and/or amylopectin; preferably at least one of potato starch, corn starch, wheat starch, sweet potato starch and tapioca starch.
According to one embodiment of the invention, the hard carbon negative electrode material is spherical particles with the particle size of 15-20 μm. The spherical particles are of a moderate size.
In order to solve the second technical problem, the invention adopts the technical scheme that:
a method of preparing the hard carbon anode material, comprising the steps of:
mixing the starch subjected to crosslinking treatment with a thermally unstable polymer to obtain a precursor;
and carrying out aromatizing treatment and carbonizing treatment on the precursor to obtain the hard carbon negative electrode material.
According to one embodiment of the invention, the polymer comprises at least one of polyethylene glycol, polyvinyl alcohol, sodium carboxymethyl cellulose, N-methyl pyrrolidone.
According to an embodiment of the present invention, the polymer may be a polymer powder or a polymer solution, and the mass percentage concentration of the polymer solution is 0.5% to 20%.
The selected polymer can form a stable chain segment structure with starch, the starch crosslinking is further promoted, and then, as the temperature of a reaction system is increased, the chain segment of the polymer part in the system can be decomposed into volatile substances, so that an irregular pore structure is formed in the hard carbon negative electrode material. With the temperature rise, the hard carbon negative electrode material can repair the pores on the surface by self-repairing, and the formation of an internal pore structure is not influenced.
The starch is composed of amylose and amylopectin, and in the crosslinking treatment process of the starch, due to poor thermal stability of the amylopectin, hydrogen bonds between the amylopectin and the amylose are broken, and the amylopectin is decomposed. After the cross-linking treatment, the polymer is added, the polymer and the starch form a stable chain segment structure again, the chain segments of the starch and the polymer move violently along with the temperature rise of a reaction system, the chain segments are broken, and the subsequent repolymerization forms an ether bond to connect the two chain segments, which is equivalent to a process for further promoting the cross-linking of the starch.
The volatile substances comprise water vapor, carbon monoxide, carbon dioxide and alkane substances.
According to one embodiment of the invention, the mass ratio of the polymer to the starch subjected to cross-linking treatment is 0.05: 1-0.5: 1. at this mass ratio, the hard carbon anode material can be synthesized.
According to one embodiment of the invention, when the polymer is a solution, the mass ratio of the polymer to the starch subjected to crosslinking treatment is 0.5: 1-2: 1; when the polymer is powder, the mass ratio of the polymer to the crosslinked starch is 0.05: 1-0.5: 1.
According to one embodiment of the present invention, the crosslinking treatment of the starch is performed under the protection of an inert gas, the inert gas is at least one of nitrogen, argon and helium, and the oxygen concentration during the crosslinking treatment of the starch is less than 200 ppm.
According to one embodiment of the invention, the starch is cross-linked at 200-235 ℃ for 8-60 h at a heating rate of 1-5 ℃/min; after the crosslinking treatment, cooling is carried out, and cooling is carried out to below 50 ℃.
The starch subjected to cross-linking treatment forms a space network structure, and a proper cross-linking agent can be added in the cross-linking process to promote the hydroxyl reaction of starch molecules, so that a plurality of starch molecules are cross-linked.
The starch which is not crosslinked expands under the condition of medium temperature, and the structure is damaged, thereby leading to the incapability of pore forming.
According to one embodiment of the invention, the temperature of the aromatizing treatment is 300-500 ℃, the time is 2-6 h, the temperature rise rate is 3-5 ℃/min, and the aromatizing treatment is carried out under the protection of inert gas, wherein the inert gas is at least one of nitrogen, argon and helium.
During the aromatic cyclization treatment, the chain segment of the polymer part in the precursor can be decomposed into volatile substances, so that an irregular pore structure is formed inside the hard carbon negative electrode material.
The method for forming the pores by using the polymer can be applied to not only a hard carbon material system, but also other carbonaceous systems, and has wide applicability.
According to one embodiment of the invention, the temperature of the carbonization treatment is 1000-1400 ℃, the time is 0.5-3 h, and the temperature rise rate is 3-5 ℃/min; and the carbonization treatment is carried out under the protection of inert gas, wherein the inert gas is at least one of nitrogen, argon and helium.
The purpose of the carbonization treatment is to calcine off excess organic matter and easily decomposed substances on the one hand and to make the hard carbon structure more stable on the other hand; when the unstable medium in the material is decomposed, the material is self-repaired at the same time, so that the structure of the material is more stable.
The starch biomass-based hard carbon material is prepared by three-step pyrolysis step-by-step sintering, the disordered interlayer structure and the large interlayer spacing of the starch biomass-based hard carbon material are favorable for the intercalation/deintercalation of sodium ions, and the starch biomass-based hard carbon material has excellent cycling stability.
In still another aspect of the present invention, there is also provided a hard carbon negative electrode comprising a copper foil and a slurry coated on the copper foil, the slurry comprising a binder, a conductive agent and the hard carbon negative electrode material.
In still another aspect of the present invention, there is also provided a sodium ion battery comprising a sodium sheet positive electrode and a hard carbon negative electrode, the hard carbon negative electrode comprising one of the hard carbon negative electrode materials.
According to one embodiment of the present invention, the average capacity of the hard carbon anode was maintained at 83% after 100 cycles at 0.1C rate.
One of the technical solutions has at least one of the following advantages or beneficial effects:
1. the pore diameter on the surface of the hard carbon negative electrode material is smaller than the internal pore of the hard carbon negative electrode material, and the sodium ions can pass through the external pore of the hard carbon negative electrode material, but because the pore diameter on the surface is very small, substances larger than ions are difficult to pass through the external pore, so that unnecessary impurities are prevented from being doped into the hard carbon negative electrode material, and the internal good sodium storage environment of the hard carbon negative electrode material is ensured. In addition, a large number of irregular pores exist in the spherical particles, so that the sodium storage capacity in the hard carbon negative electrode material can be further enhanced;
2. the starch biomass-based hard carbon material is prepared by three-step pyrolysis step-by-step sintering, the disordered interlayer structure and the large interlayer spacing of the starch biomass-based hard carbon material are favorable for the intercalation/deintercalation of sodium ions, and the starch biomass-based hard carbon material has excellent cycling stability.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is a schematic view of the internal structure of the hard carbon negative electrode material in the example.
Fig. 2 is an SEM image of the hard carbon negative electrode material in the example.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention.
The hard carbon negative electrode used in the test example includes a copper foil and a slurry coated on the copper foil, and the slurry includes a binder, a conductive agent, and a hard carbon negative electrode material.
The cell used in the test example was a sodium ion button half cell, the positive electrode was a sodium sheet, and the negative electrode was the hard carbon negative electrode described above.
Example 1
A method for preparing the hard carbon negative electrode material comprises the following steps:
(1) 50g of PEG-4000 (polyethylene glycol 4000) is dissolved in 1000ml of deionized water to prepare 5 percent PEG-4000 polymer organic pore-forming solution;
(2) under the protection of nitrogen, placing corn starch in a sintering furnace, heating to 220 ℃ at a heating rate of 1 ℃/min, carrying out crosslinking treatment for 30 hours, and cooling to 50 ℃ to obtain a primary combustion product;
(3) taking 100ml of 5% PEG-4000 polymer organic pore-forming solution obtained in the step (1) and 100g of the calcined product obtained in the step (2), and uniformly mixing the solution and the calcined product to obtain a precursor;
(4) placing the precursor obtained in the step (3) in a sintering furnace, heating to 400 ℃ at the heating rate of 3 ℃/min in the nitrogen atmosphere, and performing aromatizing treatment for 3 hours;
(5) and (3) placing the sample subjected to hole forming by aromatizing in the step (4) into a sintering furnace, heating from 400 ℃ to 1100 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, and carrying out high-temperature carbonization treatment for 2 hours to obtain the hard carbon negative electrode material.
Example 2
A method for preparing the hard carbon negative electrode material comprises the following steps:
(1) 50g of PEG-4000 is dissolved in 1000ml of deionized water to prepare 5 percent PEG-4000 polymer organic pore-forming solution;
(2) under the protection of nitrogen, placing corn starch in a sintering furnace, heating to 220 ℃ at a heating rate of 1 ℃/min, carrying out crosslinking treatment for 30 hours, and cooling to 50 ℃ to obtain a primary combustion product;
(3) taking 100ml of 5% PEG-4000 polymer organic pore-forming solution obtained in the step (1) and 100g of the calcined product obtained in the step (2), and uniformly mixing the solution and the calcined product to obtain a precursor;
(4) placing the precursor obtained in the step (3) in a sintering furnace, heating to 300 ℃ at the heating rate of 3 ℃/min in the nitrogen atmosphere, and performing aromatizing treatment for 3 hours;
(5) and (5) placing the sample subjected to hole forming by aromatizing in the step (4) into a sintering furnace, heating from 400 ℃ to 1100 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, and carrying out high-temperature carbonization treatment for 2 hours to obtain the hard carbon negative electrode material.
Example 3
A method for preparing the hard carbon negative electrode material comprises the following steps:
(1) 50g of PEG-4000 is dissolved in 1000ml of deionized water to prepare 5 percent PEG-4000 polymer organic pore-forming solution;
(2) under the protection of nitrogen, placing corn starch in a sintering furnace, heating to 220 ℃ at a heating rate of 1 ℃/min, carrying out crosslinking treatment for 30 hours, and cooling to 50 ℃ to obtain a primary combustion product;
(3) taking 100ml of 5% PEG-4000 polymer organic pore-forming solution obtained in the step (1) and 100g of the calcined product obtained in the step (2), and uniformly mixing the solution and the calcined product to obtain a precursor;
(4) placing the precursor obtained in the step (3) in a sintering furnace, heating to 500 ℃ at the heating rate of 3 ℃/min in the nitrogen atmosphere, and performing aromatizing treatment for 3 hours;
(5) and (3) placing the sample subjected to hole forming by aromatizing in the step (4) into a sintering furnace, heating from 400 ℃ to 1100 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, and carrying out high-temperature carbonization treatment for 2 hours to obtain the hard carbon negative electrode material.
Example 4
In comparison with example 1, step (2) of example 4 is: under the protection of nitrogen, placing corn starch in a sintering furnace, heating to 215 ℃ at the heating rate of 1 ℃/min for crosslinking treatment for 6 hours, continuing heating to 225 ℃ at the heating rate of 1 ℃/min for heat preservation for 12 hours, and cooling to 50 ℃ to obtain a primary combustion product. The remaining preparation steps were the same as in example 1.
Example 5
In comparison with example 1, step (2) of example 5 is: under the protection of nitrogen, placing corn starch in a sintering furnace, heating to 230 ℃ at a heating rate of 1 ℃/min, carrying out crosslinking treatment for 8 hours, and cooling to 50 ℃ to obtain a primary combustion product. The remaining preparation steps were the same as in example 1.
Example 6
In contrast to example 1, the starch of example 6 was potato starch. The preparation method is the same as that of example 1.
Example 7
In contrast to example 1, the starch of example 7 was wheat starch. The preparation method is the same as that of example 1.
Example 8
In contrast to example 1, the polymer of example 8 is polyvinyl alcohol. The preparation method is the same as that of example 1.
Example 9
In contrast to example 1, the polymer of example 9 was sodium carboxymethyl cellulose. The preparation method is the same as that of example 1.
Example 10
The polymer concentration of example 10 was different compared to example 1.
A method for preparing the hard carbon negative electrode material comprises the following steps:
(1) dissolving 100g of PEG-4000 (polyethylene glycol 4000) in 1000ml of deionized water to prepare 10% PEG-4000 polymer organic pore-forming solution;
(2) under the protection of nitrogen, placing corn starch in a sintering furnace, heating to 220 ℃ at a heating rate of 1 ℃/min, carrying out crosslinking treatment for 30 hours, and cooling to 50 ℃ to obtain a primary combustion product;
(3) taking 100ml of 10% PEG-4000 polymer organic pore-forming solution obtained in the step (1) and 100g of the calcined product obtained in the step (2), and uniformly mixing the solution and the calcined product to obtain a precursor;
(4) placing the precursor obtained in the step (3) in a sintering furnace, heating to 400 ℃ at the heating rate of 3 ℃/min in the nitrogen atmosphere, and performing aromatizing treatment for 3 hours;
(5) and (3) placing the sample subjected to hole forming by aromatizing in the step (4) into a sintering furnace, heating from 400 ℃ to 1100 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, and carrying out high-temperature carbonization treatment for 2 hours to obtain the hard carbon negative electrode material.
Example 11
The polymer concentration of example 11 was different compared to example 1.
A method for preparing the hard carbon negative electrode material comprises the following steps:
(1) 150g of PEG-4000 (polyethylene glycol 4000) is dissolved in 1000ml of deionized water to prepare 15 percent PEG-4000 polymer organic pore-forming solution;
(2) under the protection of nitrogen, placing corn starch in a sintering furnace, heating to 220 ℃ at a heating rate of 1 ℃/min, carrying out crosslinking treatment for 30 hours, and cooling to 50 ℃ to obtain a primary combustion product;
(3) taking 100ml of the 15% PEG-4000 polymer organic pore-forming solution obtained in the step (1) and 100g of the calcined product obtained in the step (2), and uniformly mixing the solution and the calcined product to obtain a precursor;
(4) placing the precursor obtained in the step (3) in a sintering furnace, heating to 400 ℃ at the heating rate of 3 ℃/min in the nitrogen atmosphere, and performing aromatizing treatment for 3 hours;
(5) and (3) placing the sample subjected to hole forming by aromatizing in the step (4) into a sintering furnace, heating from 400 ℃ to 1100 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, and carrying out high-temperature carbonization treatment for 2 hours to obtain the hard carbon negative electrode material.
Example 12
The polymer concentration of example 12 is different compared to example 1.
A method for preparing the hard carbon negative electrode material comprises the following steps:
(1) 200g of PEG-4000 (polyethylene glycol 4000) is dissolved in 1000ml of deionized water to prepare 20 percent PEG-4000 polymer organic pore-forming solution;
(2) under the protection of nitrogen, placing corn starch in a sintering furnace, heating to 220 ℃ at a heating rate of 1 ℃/min, carrying out crosslinking treatment for 30 hours, and cooling to 50 ℃ to obtain a primary combustion product;
(3) taking 100ml of the 20% PEG-4000 polymer organic pore-forming solution obtained in the step (1) and 100g of the calcined product obtained in the step (2), and uniformly mixing the solution and the calcined product to obtain a precursor;
(4) placing the precursor obtained in the step (3) in a sintering furnace, heating to 400 ℃ at the heating rate of 3 ℃/min in the nitrogen atmosphere, and performing aromatizing treatment for 3 hours;
(5) and (3) placing the sample subjected to hole forming by aromatizing in the step (4) into a sintering furnace, heating from 400 ℃ to 1100 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, and carrying out high-temperature carbonization treatment for 2 hours to obtain the hard carbon negative electrode material.
Comparative example 1
Placing 100g of corn starch at 230 ℃ for crosslinking treatment for 8 hours to obtain a starch precursor; and (3) placing the starch precursor at 400 ℃ for 2 hours of aromatizing treatment, performing high-temperature carbonization treatment at 1100 ℃ for 3 hours, and cooling to room temperature to obtain the hard carbon material.
Comparative example 1 since the raw material for preparation does not contain polymer, there is almost no void in the hard carbon material of the final product.
Comparative example 2
In contrast to example 1, the polymer of comparative example 2 was phenolic 2123. The preparation method is the same as that of example 1.
Comparative example 2 since the polymer having better thermal stability was selected, the final product hard carbon material was almost free of voids.
And (3) performance testing:
the schematic diagram of the internal structure of the hard carbon negative electrode material is shown in fig. 1, the internal structure is a disordered interlayer structure, and the external part of the hard carbon negative electrode material is distributed with a micropore structure.
An SEM image (scanning electron microscope image) of the hard carbon negative electrode material prepared in example 1 is shown in fig. 2, and the hard carbon negative electrode material is spherical particles having a particle size of 15 to 20 μm.
Table 1 shows specific surface areas of the hard carbon products prepared in examples 1, 2 and 3 and comparative example 1, and specific data are obtained by a bestseder specific surface area tester.
TABLE 1 specific surface area of hard carbon products
As is clear from Table 1, the hard carbon products prepared in examples 1 to 3 had a lower specific surface area than comparative example 1, and in particular example 1, had a specific surface area of only 0.436m2/g。
When the starch is not subjected to pore forming, certain natural defects exist on the surface, so that the specific surface area is larger, after the polymer is added into the starch for pore forming, the structure of the starch is changed to a certain extent, gaps appear inside the starch, and the surface defects can be automatically repaired, so that the specific surface area is reduced.
Comparative example 1 was prepared without the addition of the corresponding polymer, i.e. without the binding of starch to the polymer, and even without the step of breaking down the segments of the polymer part of the system during the heating, thus forming a pore structure.
In the examples 1 to 3, although the starch biomass-based hard carbon material is prepared by sintering through three-step pyrolysis method, the sintering temperature is different, and the system reaction is different, so that the product structure is different, and the sizes of the internal and external pores of the hard carbon material are different.
Table 2 shows the electrochemical properties of the hard carbon negative electrodes of the sodium-ion batteries prepared in examples 1, 2 and 3 and comparative example 1, and the specific data are obtained by testing through a blue test cabinet.
Table 2 comparison of electrochemical performance of hard carbon cathode for sodium ion battery
As can be seen from table 2, the electrochemical properties of the hard carbon product prepared in the example are better than those of comparative example 1, especially example 1. The hard carbon product of comparative example 1, which has an excessively large specific surface area, consumes a part of sodium ions to form a solid electrolyte film, resulting in low first charge-discharge efficiency and first discharge specific capacity.
The above description is only an example of the present invention and is not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention as described in the specification of the present invention or directly or indirectly applied to the related technical fields are included in the scope of the present invention.
Claims (10)
1. A hard carbon anode material characterized in that:
the substrate of the hard carbon negative electrode material is prepared by taking starch as a raw material;
the diameter of the internal pores of the hard carbon negative electrode material is larger than the diameter of the surface pores.
2. The hard carbon anode material according to claim 1, wherein: the starch is amylose and/or amylopectin; preferably at least one of potato starch, corn starch, wheat starch, sweet potato starch and tapioca starch.
3. The hard carbon anode material according to claim 1, wherein: the hard carbon negative electrode material is spherical particles with the particle size of 15-20 mu m.
4. The hard carbon negative electrode material according to claim 1, characterized in that: the diameter of the internal pore is X, and X is more than 0 and less than or equal to 5 nm.
5. A method of preparing a hard carbon anode material according to any one of claims 1 to 4, characterized in that: the method comprises the following steps:
mixing the starch subjected to crosslinking treatment with a thermally unstable polymer to obtain a precursor;
and carrying out aromatizing treatment and carbonizing treatment on the precursor to obtain the hard carbon negative electrode material.
6. The method of claim 5, wherein: the polymer comprises at least one of polyethylene glycol, polyvinyl alcohol, sodium carboxymethyl cellulose and N-methyl pyrrolidone.
7. The method of claim 5, wherein: the mass ratio of the polymer to the starch subjected to cross-linking treatment is 0.05: 1-0.5: 1.
8. the method of claim 5, wherein: the temperature of aromatic cyclization treatment is 300-500 ℃, and the time is 2-6 h.
9. The method of claim 5, wherein: the carbonization treatment is carried out at the temperature of 1000-1400 ℃ for 0.5-3 h.
10. A sodium ion battery, characterized by: comprising a sodium sheet positive electrode and a hard carbon negative electrode comprising a hard carbon negative electrode material as claimed in any one of claims 1 to 4.
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| PCT/CN2022/116262 WO2023098191A1 (en) | 2021-12-01 | 2022-08-31 | Hard carbon negative electrode material, and preparation method therefor and use thereof |
| DE112022002661.8T DE112022002661T5 (en) | 2021-12-01 | 2022-08-31 | NEGATIVE HARD CARBON ELECTRODE MATERIAL AND PRODUCTION METHOD AND USE THEREOF |
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| WO2024007461A1 (en) * | 2022-07-08 | 2024-01-11 | 广东邦普循环科技有限公司 | Hard carbon material, preparation method therefor and use thereof |
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