CN108439363A - Sodium-ion battery hard carbon cathode material based on biomass - Google Patents
Sodium-ion battery hard carbon cathode material based on biomass Download PDFInfo
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- CN108439363A CN108439363A CN201810159334.1A CN201810159334A CN108439363A CN 108439363 A CN108439363 A CN 108439363A CN 201810159334 A CN201810159334 A CN 201810159334A CN 108439363 A CN108439363 A CN 108439363A
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- 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
Sodium-ion battery hard carbon cathode material based on biomass.The preparation method of the negative material includes：Biological raw material tamarind shell is provided and is cleaned；Tamarind shell after vacuum drying cleaning；Tamarind shell after drying is crushed and obtains granular precursor；It is heat-treated granular precursor under inert atmosphere；It grinds the granular precursor after heat treatment and obtains hard carbon dusty material；Gained hard carbon dusty material is added in hydrochloric acid solution, ultrasonic disperse, stirring is stood；The lower sediment thing after standing is taken to carry out eccentric cleaning；And processing is dried to obtain sodium-ion battery hard carbon cathode material to the sediment after eccentric cleaning.The present invention selects tamarind shell to prepare biomass hard carbon material and carries out above-mentioned process, raw material sources are extensive, preparation process is simple, at low cost, environmental-friendly, prepared hard carbon material has good removing sodium, embedding sodium ability, reversible charge-discharge performance is good, and capacity retention ratio still can be 90% or more after cycle charge-discharge 200 weeks.
Description
Technical field
The present invention relates to a kind of anode material of lithium-ion batteries.
Background technology
The prosperity and development of modern society be unable to do without the development and utilization of fossil energy, but largely use conventional fossil energy for a long time
While source offers convenience to us, a series of environmental problem is also brought, such as air pollution, global warming, extreme weather frequency
Hair etc. and the problem of resource exhaustion increasingly.Countries in the world all put into great effort exploitation, utilization, storage, conversion, wind thus
The renewable and clean energy resources such as energy, solar energy, tide energy, geothermal energy.Secondary cell is the storage energy more than needed and realizes that the energy turns
The advanced technology of change, and by the extensive concern of countries in the world.Compared with lithium ion battery, sodium-ion battery relies on sodium reserves
Greatly, the advantages that at low cost, becomes a competitive candidate of large-scale energy storage system.Developing low-cost electrode material is
The key of sodium-ion battery development, inexpensive hard carbon cathode material are worth with important research.
The study found that hard carbon with stable structure, as sodium ion battery electrode material when with the charge and discharge cycles longevity
The advantages that life is long, reversible specific capacity is high, voltage platform is low, cycle performance and high rate performance are good, security performance is high.And with biology
Matter then has both for hard carbon prepared by raw material to be derived from a wealth of sources, prepares feature simple, at low cost.Generally by the way that be simply pyrolyzed can
Obtain inheriting the hard carbon material of biomass presoma natural topography.
A kind of sodium ion based on biomass such as pine nut, walnut shell, rice husks disclosed in Chinese patent CN 106299365A is used
Hard carbon cathode material, preparation method and sodium-ion battery, biomass material is crushed, pre-burning, and rear calcining cooling prepares intermediate,
Handled again with acid solution after base extraction, after by microwave activation process the hard carbon cathode material that suitable sodium-ion battery uses has been made
Material.A kind of sodium-ion battery use of the hard carbon graphite based on mangosteen shell biology mass shell disclosed in Chinese patent CN 107068997
Carbon containing biological mass shell powder is added in alkaline solution, seals hydro-thermal by anode material, preparation method and sodium-ion battery,
It is mixed with powdered graphite after pickling, washing, ball milling refinement, pickling after high temperature cabonization, drying, grinding obtains hard carbon/graphene
Composite material can be used for sodium-ion battery.But above-mentioned preparation method is complex, and material processing mode is relatively complicated, certain
The cost of large-scale production and application is increased in degree.Therefore simple, convenience and high-efficiency technology of preparing that there is an urgent need for development technologies.
Invention content
It is an object of the present invention to provide a kind of hard carbon cathode materials, and it is suitable for sodium-ion batteries, and can overcome above-mentioned carry
And certain or certain defects.
According to the first aspect of the invention, a kind of preparation method of sodium-ion battery hard carbon cathode material is provided, including：
Biological raw material tamarind shell is provided；
Tamarind shell is cleaned using deionized water；
Tamarind shell under the conditions of 60~120 DEG C after vacuum drying cleaning 8~24 hours；
Tamarind shell after drying is crushed and obtains granular precursor；
Granular precursor is heat-treated under inert atmosphere, wherein heat treatment temperature is 800 DEG C to 1300 DEG C, from from room temperature to heat
It is 5 DEG C/min or so to manage the heating rate of temperature and the rate of temperature fall from heat treatment temperature to room temperature, and constant temperature is being heat-treated
The heat treatment time of temperature is 0.5~5 hour；
It grinds the granular precursor after heat treatment and obtains hard carbon dusty material；
Gained hard carbon dusty material is added in the hydrochloric acid solution of 0.5~2mol/L, ultrasonic disperse, is stirred 1~3 hour
Stand 12~36 hours afterwards；
The lower sediment thing after standing is taken to carry out eccentric cleaning；And
Processing is dried to obtain sodium-ion battery hard carbon cathode material to the sediment after eccentric cleaning.
Centrifuge speed can be 2000~4200rpm when preparation in accordance with the present invention, wherein eccentric cleaning, preferably
Rotating speed is 3000rpm, is repeated 3~5 times.
Preparation in accordance with the present invention, when being related to being dried, such as when handling drying precipitate, temperature is 60
~120 DEG C, the time be 8~24 hours；It is 12 hours dry at preferably 80 DEG C.
Preparation in accordance with the present invention, wherein heat treatment is preferably two-part heat treatment, the heat treatment temperature of first segment
It it is 800 DEG C to 1000 DEG C, constant temperature heat treatment time is 1~2 hour；The heat treatment temperature of second segment is 1200 DEG C to 1300 DEG C,
Constant temperature heat treatment time is 10~30 minutes, and the heating rate in entire heat treatment process is identical with rate of temperature fall, be 5 DEG C/
Min or so.
The present invention, as biological raw material, is preferably used above-mentioned two stage process technique according to its characteristic, shown using tamarind shell
Work enhances its removing sodium and embedding sodium ability, to improve the activity of negative electrode active material.
Preparation in accordance with the present invention, wherein grinding granular precursor is preferably ground 1~2 hour in grinding alms bowl.
Preparation in accordance with the present invention, it is preferable to use 1.0mol/L hydrochloric acid come handle gained hard carbon dusty material, from
And promote the cycle performance and high rate performance of material.
According to another aspect of the present invention, a kind of sodium-ion battery is provided, including according to prepared by above-mentioned negative material
Cathode and electrolyte, wherein electrolyte include be selected from NaClO4、NaPF6, NaTFSI and NaBF4Sodium salt and be selected from carbonic acid
The nonaqueous solvents of vinyl acetate, diethyl carbonate, propene carbonate, dimethyl carbonate, diethylene glycol dimethyl ether and glycol dimethyl ether.
Sodium-ion battery according to the present invention, electrolyte preferably contain 1M NaClO4Ethylene carbonate (EC) and carbon
Both diethyl phthalates (DEC), wherein ethylene carbonate (EC) and diethyl carbonate (DEC) volume ratio is 1:1.
Sodium-ion battery according to the present invention, wherein cathode are by above-mentioned hard carbon cathode material, acetylene black and binder (example
Such as Kynoar (PVDF)) with mass ratio 8:1:After 1 ratio uniform grinding with solvent (such as N-methyl pyrrolidones
(NMP)) negative electrode slurry is made after mixing, and coated in obtained on copper foil current collector.
The present invention has the following advantages：
Selecting biomass hard carbon material prepared by tamarind shell has good removing sodium, embedding sodium ability；
Raw material sources are extensive, preparation process is simple, at low cost, environmental-friendly；
The reversible charge-discharge performance of prepared hard carbon material is good, and capacity retention ratio still may be used after cycle charge-discharge 200 weeks
90% or more.
Description of the drawings
Fig. 1 is the TEM collection of illustrative plates according to 800-H hard carbons dusty material made from embodiment 1；
Fig. 2 is the TEM collection of illustrative plates according to 900/1250-H hard carbons dusty material made from embodiment 4；
Fig. 3 is the XRD diagram according to 1000-H and 1000-R hard carbon dusty materials made from embodiment 2 and comparative example 2 respectively
Spectrum；And
Fig. 4 is the voltage range and 50mAg in 0.1-2.5V according to battery made from test example 2-1Current density under follow
200 weeks cycle performance figures of ring.
Specific implementation mode
The present invention is further illustrated below in conjunction with the accompanying drawings.
Comparative example 1
(1) pretreatment of biological material tamarind shell：Tamarind shell is put into container, appropriate amount of deionized water, ultrasound is added
Processing 1 hour replaces dust, the dirt on deionized water cleaning shell surface, is cleaned with deionized water and become for several times to deionized water
It obtains limpid and there is no shell residue；Container equipped with tamarind shell is put at 80 DEG C of vacuum drying chamber 12 hours dry；
(2) by the tamarind shell shearing-crushing of drying at particle；
(3) the tamarind fragment in step (2) is put into crucible, is placed in vacuum tube furnace, under argon atmosphere protection
It is warming up to 800 DEG C with the rate of 5 DEG C/min, constant temperature 2 hours, then be cooled to room temperature with phase same rate, sample is taken out, centre is obtained
Product；
(4) sample in step (3) is put into mortar to grind and obtains within 1~2 hour dusty material, mark 800-R；
Comparative example 2
Therefore step (1) to (4) with comparative example 1, the difference is that being warming up to 1000 DEG C in step (3), and exists substantially
Label is in step (4)；
XRD tests are carried out to the hard carbon powder 1000-R that comparative example 2 is prepared, XRD spectrum is as shown in Figure 3.
Comparative example 3
Therefore step (1) to (4) with comparative example 1, the difference is that being warming up to 1200 DEG C in step (3), and exists substantially
Label is in step (4)；
Comparative example 4
Step (1) to (4) is substantially with comparative example 1, the difference is that it is small to be first warming up to 900 DEG C of processing 2 in step (3)
When, it then proceedes to be warming up to 1250 DEG C with 5 DEG C/min rates and handles 20 minutes, and therefore label is in the step (4)
1250-R；
Embodiment 1
Step (1) to (4) is a difference in that substantially with comparative example 1 on the basis of step (4)：
Dusty material in step (4) is taken to be added in the hydrochloric acid solution of a concentration of 1.0mol/L, ultrasound makes material disperse in 1 hour
Uniformly；Stirring 2 hours；After standing 24 hours, supernatant liquid is outwelled, lower sediment thing deionized water eccentric cleaning 3 is taken
It is secondary, the sample that cleaning is completed is put into vacuum drying chamber drying 12 hours at 80 DEG C, acidification hard carbon material is obtained, marks 800-
H；
TEM tests are carried out to hard carbon powder 800-H made from embodiment 1, TEM collection of illustrative plates is as shown in Figure 1.
Embodiment 2
Therefore step (1) to (4) with embodiment 1, the difference is that being warming up to 1000 DEG C in step (3), and exists substantially
Label is in step (4)；
XRD tests are carried out to the hard carbon powder 1000-H that embodiment 2 is prepared, XRD spectrum is as shown in Figure 3.
Embodiment 3
Therefore step (1) to (4) with embodiment 1, the difference is that being warming up to 1200 DEG C in step (3), and exists substantially
Label is in step (4)；
Embodiment 4
Step (1) to (4) is substantially with embodiment 1, the difference is that it is small to be first warming up to 900 DEG C of processing 2 in step (3)
When, it then proceedes to be warming up to 1250 DEG C with 5 DEG C/min rates and handles 20 minutes, and therefore label is in the step (4)
1250-H；
TEM tests are carried out to hard carbon powder 900/1250-H made from embodiment 4, TEM collection of illustrative plates is as shown in Figure 2.
Comparative experimental example 1
(1) use smear method by hard carbon dusty material 800-R, acetylene black, binder Kynoar made from comparative example 1
(PVDF) with mass ratio 8:1:1 ratio uniform is mixed with solvent N-methyl pyrrolidones (NMP), uniformly grinding 1 hour, system
Negative electrode slurry is obtained, is coated on copper foil current collector, and is put into vacuum drying chamber at 80 DEG C 12 hours dry；Using roller
Pressure, cuts out to obtain hard carbon cathode pole piece.
(2) the uniform complete pole piece that selected part is cut, is weighed, and calculate the quality of active material using precision balance
((total-m copper of m) * 0.8)；Made to electrode and reference electrode with sodium piece, in the glove box under argon atmosphere, by correctly operation
Step is assembled into together with anode cover, negative electrode casing, fibreglass diaphragm, sodium piece (diameter 12mm* thickness is 1mm), electrolyte
CR2032 type button cells.Electrolyte used is dissolved with 1M NaClO4Ethylene carbonate (EC) and diethyl carbonate
(DEC) (the two volume ratio is 1:1) mixed liquor is sealed assembled battery using buckle battery mouth sealer, from hand
Casing takes out, and 24 hours are stood under room temperature.
Comparative experimental example 2-4
According to the method assembled battery of test example 1, the difference is that, negative material is respectively using hard carbon powder obtained by comparison 2-4
Powder material 1000-R, 1200-R, 900/1250-R.
Test example 1-4
According to the method assembled battery of comparative experimental example 1, the difference is that, negative material is used respectively obtained by embodiment 1-4
Hard carbon dusty material 800-H, 1000-H, 1200-H, 900/1250-H.
Performance test
(1) electrochemical property test is carried out to sodium-ion battery made from test example 1-4 and comparative experimental example 1-4 respectively,
Test is to be set as 200 in LAND CT2001A testers (Wuhan Land Electronic Co., Ltd.) the test loop period using instrument
Week, specifically：In the voltage range and 50mAg of 0.1-2.5V-1Current density under, by battery charging and discharging recycle 200 weeks；Detection
Charge specific capacity (mAhg after the completion of activation-1) and charge specific capacity (mAhg of the charge and discharge cycles after 200 weeks-1), and calculate and fill
200 weeks capacity retention ratios of discharge cycles (the charging specific volume of=charge and discharge cycles after 200 weeks after the completion of charge specific capacity ÷ activation
Amount × 100%), result is remembered in table 1.
(2) by taking test example 2 as an example, sodium-ion battery obtained is recycled to cycle performance exhibition in 200 weeks under test conditions
It is shown in Fig. 4, from fig. 4, it can be seen that under the conditions of the charge and discharge, battery can stablize cycle 200 weeks.
Table 1
By test example 1 and comparative experimental example 1 comparison (test example 2 and comparative experimental example 2, test example 3 and comparative experimental example 3,
Test example 4 and comparative experimental example 4) it can be found that the charge specific capacity of material after HCl treatment and the capacity after 200 weeks are protected
Holdup is apparently higher than unacidified material, illustrates after HCl treatment the cycle performance of material and stability is firm is promoted.
Test example 1,2,3,4 and comparative experimental example 1,2,3,4 are compared, it can be found that being heat-treated using two-part
Biological material charge specific capacity higher.Sample 900/1250-H battery performances are better than other three similar acidifications in the present invention
Sample；Similarly, the battery performance of sample 900/1250-R is also better than other three similar not-acidified processing samples.Pass through analysis
Fig. 1 and Fig. 2 it can be found that sample 900/1250-H crystallinity of the crystallinity also above sample 800-H.
Claims (5)
1. a kind of preparation method of sodium-ion battery hard carbon cathode material, including：
Biological raw material tamarind shell is provided；
Tamarind shell is cleaned using deionized water；
Tamarind shell under the conditions of 60~120 DEG C after vacuum drying cleaning 8~24 hours；
Tamarind shell after drying is crushed and obtains granular precursor；
Granular precursor is heat-treated under inert atmosphere, wherein heat treatment temperature is 800 DEG C to 1300 DEG C, from room temperature to heat treatment temperature
The heating rate of degree and rate of temperature fall from heat treatment temperature to room temperature are 5 DEG C/min or so, and constant temperature is in heat treatment temperature
Heat treatment time be 0.5~5 hour；
It grinds the granular precursor after heat treatment and obtains hard carbon dusty material；
Gained hard carbon dusty material is added in the hydrochloric acid solution of 0.5~2mol/L, ultrasonic disperse, it is quiet after stirring 1~3 hour
It sets 12~36 hours；
The lower sediment thing after standing is taken to carry out eccentric cleaning；And
Processing is dried to obtain sodium-ion battery hard carbon cathode material to the sediment after eccentric cleaning.
2. centrifuge speed is 2000~4200rpm, weight when preparation method, wherein eccentric cleaning according to claim 1
It is 3~5 times multiple.
3. preparation method according to claim 1, the temperature to drying precipitate processing is 60~120 DEG C, the time be 8~
24 hours.
4. preparation method according to claim 1 is heat-treated, the heat treatment temperature of first segment wherein heat treatment is two-part
It it is 800 DEG C to 1000 DEG C, constant temperature heat treatment time is 1~2 hour；The heat treatment temperature of second segment is 1200 DEG C to 1300 DEG C,
Constant temperature heat treatment time is 10~30 minutes, and the heating rate in entire heat treatment process is identical with rate of temperature fall, be 5 DEG C/
Min or so.
5. a kind of sodium-ion battery includes the cathode prepared by the negative material according to one of claim 1-4 and electrolysis
Liquid, wherein electrolyte include to be selected from NaClO4、NaPF6, NaTFSI and NaBF4Sodium salt and selected from ethylene carbonate, carbonic acid two
The nonaqueous solvents of ethyl ester, propene carbonate, dimethyl carbonate, diethylene glycol dimethyl ether and glycol dimethyl ether.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109592660A (en) * | 2018-11-22 | 2019-04-09 | 上海杉杉科技有限公司 | A kind of hard carbon presoma using carbon containing biological mass shell preparation, hard carbon/graphite composite material and its preparation method and application |
| CN109755531A (en) * | 2019-01-09 | 2019-05-14 | 电子科技大学 | Porous carbon based on tamarind shell-sulphur composite material and preparation method and purposes |
| CN110809558A (en) * | 2018-11-23 | 2020-02-18 | 辽宁星空钠电电池有限公司 | Defect-rich sodium ion battery negative electrode material and preparation method and application thereof |
| CN111847418A (en) * | 2019-04-24 | 2020-10-30 | 香港理工大学深圳研究院 | Preparation method and application of biomass hard carbon for negative electrode material of sodium-ion battery |
| CN112537765A (en) * | 2020-11-17 | 2021-03-23 | 浙江大学自贡创新中心 | Preparation method of carbon negative electrode material of lithium ion battery |
| CN113044827A (en) * | 2021-03-16 | 2021-06-29 | 昆山昆鹏利杰高分子材料技术有限公司 | Nano carbon material composite biomass hard carbon electrode material and preparation method and application thereof |
| CN114890404A (en) * | 2022-05-31 | 2022-08-12 | 温州大学碳中和技术创新研究院 | Preparation method of bamboo charcoal capable of being produced in large scale and application of bamboo charcoal in sodium ion battery |
| CN115353090A (en) * | 2022-08-11 | 2022-11-18 | 华南理工大学 | Novel biomass hard carbon sodium ion battery material and preparation method thereof |
| WO2023050466A1 (en) * | 2021-09-29 | 2023-04-06 | 海南大学 | Method for preparing hard carbon negative electrode of lithium/sodium ion battery by using biomass charcoal |
| CN117293312A (en) * | 2023-11-24 | 2023-12-26 | 深圳市贝特瑞新能源技术研究院有限公司 | Hard carbon material, preparation method and application thereof, and sodium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109592660A (en) * | 2018-11-22 | 2019-04-09 | 上海杉杉科技有限公司 | A kind of hard carbon presoma using carbon containing biological mass shell preparation, hard carbon/graphite composite material and its preparation method and application |
| CN110809558A (en) * | 2018-11-23 | 2020-02-18 | 辽宁星空钠电电池有限公司 | Defect-rich sodium ion battery negative electrode material and preparation method and application thereof |
| WO2020103139A1 (en) * | 2018-11-23 | 2020-05-28 | 辽宁星空钠电电池有限公司 | Sodium ion battery negative electrode material rich in defects, preparation method therefor and application thereof |
| CN109755531B (en) * | 2019-01-09 | 2022-02-08 | 电子科技大学 | Porous carbon-sulfur composite material based on acid horn shell and preparation method and application thereof |
| CN109755531A (en) * | 2019-01-09 | 2019-05-14 | 电子科技大学 | Porous carbon based on tamarind shell-sulphur composite material and preparation method and purposes |
| CN111847418A (en) * | 2019-04-24 | 2020-10-30 | 香港理工大学深圳研究院 | Preparation method and application of biomass hard carbon for negative electrode material of sodium-ion battery |
| CN112537765A (en) * | 2020-11-17 | 2021-03-23 | 浙江大学自贡创新中心 | Preparation method of carbon negative electrode material of lithium ion battery |
| CN113044827A (en) * | 2021-03-16 | 2021-06-29 | 昆山昆鹏利杰高分子材料技术有限公司 | Nano carbon material composite biomass hard carbon electrode material and preparation method and application thereof |
| WO2023050466A1 (en) * | 2021-09-29 | 2023-04-06 | 海南大学 | Method for preparing hard carbon negative electrode of lithium/sodium ion battery by using biomass charcoal |
| CN114890404A (en) * | 2022-05-31 | 2022-08-12 | 温州大学碳中和技术创新研究院 | Preparation method of bamboo charcoal capable of being produced in large scale and application of bamboo charcoal in sodium ion battery |
| CN115353090A (en) * | 2022-08-11 | 2022-11-18 | 华南理工大学 | Novel biomass hard carbon sodium ion battery material and preparation method thereof |
| CN117293312A (en) * | 2023-11-24 | 2023-12-26 | 深圳市贝特瑞新能源技术研究院有限公司 | Hard carbon material, preparation method and application thereof, and sodium ion battery |
| CN117293312B (en) * | 2023-11-24 | 2024-03-12 | 深圳市贝特瑞新能源技术研究院有限公司 | Hard carbon material, preparation method and application thereof, and sodium ion battery |
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