CN108975304A - Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material and its preparation method and application - Google Patents
Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material and its preparation method and application Download PDFInfo
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- CN108975304A CN108975304A CN201810853591.5A CN201810853591A CN108975304A CN 108975304 A CN108975304 A CN 108975304A CN 201810853591 A CN201810853591 A CN 201810853591A CN 108975304 A CN108975304 A CN 108975304A
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- prickly ash
- chinese prickly
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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
The present invention provides a kind of Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material and its preparation method and application, comprising steps of 1, collect Chinese prickly ash, wash and dry processing；It 2, will treated that Chinese prickly ash is placed in tube furnace is carbonized in advance under inert gas protection, high temperature cabonization and annealing；3, Chinese prickly ash carbon lye after annealing, acid solution, water successively washs, Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material is obtained after drying, the present invention can make full use of a large amount of existing chafing dishes to discard the Chinese prickly ash waste residue in the bottom of a pan, these are inexpensive with wild pepper seed useless when production Chinese prickly ash, high carbon containing material, Chinese prickly ash waste residue is set to become the ideal persursor material of synthesis hard carbon, the biomass hard carbon that the present invention prepares, it can effectively improve deintercalation ability of the sodium ions to potassium ions in cathode, with high coulombic efficiency for the first time (80.4%), to improve the capacity of sodium-ion battery, Chinese prickly ash waste residue is from a wealth of sources, it is low in cost, it is the perfect substitute of traditional mode of production hard carbon persursor material.
Description
Technical field
The invention belongs to energy storage material and electrochemical technology field, especially a kind of Chinese prickly ash hard carbon sodium ions to potassium ions cathode material
Material and its preparation method and application.
Background technique
It is developed from a large amount of lithium electric material of the successful commercialization of the lithium ion battery nineties in last century (LIB), lithium ion
The development of battery enters a fast-developing epoch.Lithium ion battery because its operating voltage with higher, higher capacity,
The features such as self discharge is small, power-performance is good and has extended cycle life, has been widely used in various electronic products.However, into
21 century leads to the continuous rise of lithium resource price due to carrying out the ion battery of change of large-scale commercial applications.Therefore, to sodium (potassium)
The research of ion battery is taken seriously again.Metallic sodium, potassium and lithium are in same main group, three's difference in the periodic table of elements
It is smaller, all have and is used as rocking chair type secondary metals cell potential.
For the positive electrode of embedding sodium (potassium), has the research report of feasibility so far, such as containing the transiting metal oxidation of sodium
Object and transition metal fluorophosphoric acid sodium salt.All there is good voltage platform and cheap price.But for the cathode of embedding sodium (potassium)
The research of material is relatively fewer, mainly has the graphite material interlamellar spacing of good embedding lithium behavior smaller (0.335nm), biggish
Sodium ion can not be effectively embedded in and deintercalation, and when being used for kalium ion battery cathode, it is embedded in the high rate performance and difference of graphite.Therefore
Realize reversible sodium (potassium) ion be effectively embedded into and deintercalation, it is crucial for being prepared with larger interlamellar spacing carbon material.
Amorphous hard carbon is generally divided into easy graphited soft carbon and is difficult to graphited hard according to graphitization complexity
Carbon, and hard carbon material becomes sodium (potassium) ion of most application prospect due to having many advantages, such as that specific capacity is high, storage sodium voltage is high
Cell negative electrode material.However, the carbon source of production hard carbon is mainly organic matter, such as phenolic resin, formaldehyde at present, higher cost,
And the poor circulation of obtained hard carbon, the problems such as high rate performance is poor, and first circle capacity is lower, it is limited as sodium (potassium) ion
The extensive use of cell negative electrode material.
Summary of the invention
In view of the defects in the background art, the present invention proposes a kind of Chinese prickly ash hard carbon sodium ions to potassium ions cell negative electrode materials
And its preparation method and application.In the method for preparation sodium ions to potassium ions cell negative electrode material proposed by the present invention, it is prepared for having micro-
What brilliant graphene was piled up, porous, the porous hard carbon with larger interlamellar spacing, this special porous-micro- graphite crystal structure, energy
The deintercalation ability of sodium (potassium) ion is effectively improved, the capacity and multiplying power of sodium (potassium) ion battery are improved.
In view of the foregoing deficiencies of prior art, it is an object of the invention to solve the problems, such as, a kind of Chinese prickly ash hard carbon is provided
Sodium ions to potassium ions negative electrode material and its preparation method and application.
For achieving the above object, technical solution of the present invention is as follows:
A kind of preparation method of Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material, comprising the following steps:
Step 1 collects Chinese prickly ash first, washes and dries processing；
Step 2, by treated, Chinese prickly ash is placed in tube furnace under the protection of inert gas is carbonized in advance, pyrocarbon
Change and makes annealing treatment；
Chinese prickly ash carbon lye, acid solution, water after step 3, annealing successively wash, obtained after drying Chinese prickly ash hard carbon sodium/potassium from
Sub- negative electrode material.
It is preferred that the Chinese prickly ash be Pericarpium Zanthoxyli or cooked Chinese prickly ash waste material, including pricklyash hull, wild pepper seed its
At least one of.
It is preferred that when being cleaned in step 1 by Chinese prickly ash be placed in water, ethyl alcohol, methanol, in acetone it is one or several kinds of mixed
It closes cleaning in solution and removes surface grease, cleaning liquid temperature is 10-100 DEG C.
It is preferred that carbonization is preceding in advance in step 2 carries out independent pickling or independent alkali cleaning or first alkali to Chinese prickly ash
Rear pickling is washed, lye is selected from potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, and acid solution is selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid；
The hydroxyl concentration of lye be 0.3-1mol L, the hydrogen ion concentration of acid solution be 0.5-3mol L, wash time is that 1-10 is small
When, wash temperature is 10-90 DEG C.
It is preferred that the temperature being carbonized in advance in step 2 is 200-500 DEG C, atmosphere be argon gas or nitrogen or air,
Or the gaseous mixture of argon gas and nitrogen, soaking time are 0.5-5 hours.
It is preferred that the temperature of step 2 high temperature carbonization is 600-2000 DEG C, heating rate is 1-20 DEG C/min,
Atmosphere is the gaseous mixture of argon gas or nitrogen or air or argon gas and nitrogen, gas flow rate 5-300CC/min, soaking time
It is 1-5 hours.
It is preferred that when making annealing treatment in step 2, annealing temperature is 200-500 DEG C, heating rate is 1-20 DEG C/
Min, atmosphere are the gaseous mixture of argon gas or nitrogen or air or argon gas and nitrogen, and gas flow rate is in 5-300CC/min, heat preservation
Time is 0.5-5 hours.
It is preferred that the Chinese prickly ash carbon elder generation alkali cleaning after annealing in step 3, rear pickling, are finally washed to neutrality, lye choosing
From potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, acid solution is selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid；The hydroxyl of lye is dense
Degree be 0.3-5mol L, the hydrogen ion concentration of acid solution be 0.5-5mol L, wash time is 1-10 hours, wash temperature 10-
90℃。
Preferably, conductive agent, binder can be also added in the Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material after drying, wherein spending
The mass ratio of green pepper carbon is 10%-100%.
For achieving the above object, the present invention also provides a kind of a kind of Chinese prickly ash hard carbons obtained using above-mentioned preparation method
Sodium ions to potassium ions negative electrode material.
For achieving the above object, the present invention also provides a kind of above-mentioned Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode materials to be used for
The purposes of sodium ions to potassium ions battery electrode.
The invention has the benefit that the present invention provides a kind of Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material and its preparations
Method confirms that recycling Chinese prickly ash can be as the persursor material for preparing hard carbon for the first time.The present invention can make full use of a large amount of existing
Chafing dish discards the Chinese prickly ash waste residue in the bottom of a pan, and produces these inexpensive, high carbon containing materials of wild pepper seed useless when Chinese prickly ash, so that
Chinese prickly ash waste residue becomes the ideal persursor material of synthesis hard carbon.Based on the above feature, the biomass hard carbon that the present invention prepares, energy
Be effectively improved deintercalation ability of the sodium ion in cathode, have high coulombic efficiency for the first time (80.4%), thus improve sodium from
The capacity of sub- battery.Further, Chinese prickly ash waste residue is from a wealth of sources, low in cost, is that traditional mode of production hard carbon persursor material is perfect
Substitute, and the method for the present invention is easy to operate, reproducible, has the value of environmental protection and application value.
Detailed description of the invention
Fig. 1 is that charge and discharge cycles of the obtained anode material of lithium-ion battery of the embodiment of the present invention 1 under 0.1C multiplying power are bent
Line；
Fig. 2 is that first circle charge and discharge of the obtained anode material of lithium-ion battery of the embodiment of the present invention 2 under 0.1C multiplying power are bent
Line.
Fig. 3 is charging and discharging curve of the obtained kalium ion battery negative electrode material of the embodiment of the present invention 3 under different multiplying.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Table 1 is for the first time coulombic efficiency comparison of the hard carbon of different carbon source preparation under 0.1C multiplying power
| Carbon source | First circle coulombic efficiency |
| Chinese prickly ash waste residue | 80.4% |
| Banana skin | 68.2% |
| Pomelo peel | 66% |
Embodiment 1
A method of anode material of lithium-ion battery is prepared using Chinese prickly ash waste material, comprising the following steps:
Step 1: the collection cooked chafing dish waste material containing pricklyash hull, wild pepper seed of chafing dish first is placed in water and ethyl alcohol and adds
Thermal cleaning removes surface grease, and cleaning liquid temperature is 100 DEG C, and the substance outside cleaning removal Chinese prickly ash, obtained product is in baking oven
In 70 DEG C of dry 12h, to remove moisture removal；
Step 2: independent pickling being carried out to Chinese prickly ash before pre- carbonization, acid solution is selected from hydrochloric acid；The hydrogen ion concentration of acid solution is
0.5mol L, wash time is 1 hour, and wash temperature is 10 DEG C.
Step 3: the sample after drying is put into tube furnace, under the protection of argon gas, with the heating rate of 5 DEG C/min by
Room temperature is carbonized in advance to 500 DEG C, and 5h is kept the temperature, and after the completion, with furnace cooled to room temperature, is taken out；
Step 4: sample being put into tube furnace, atmosphere is argon gas, gas flow rate 5-300CC/min, with 20 DEG C/min
Heating rate by room temperature to 2000 DEG C of progress high temperature cabonizations, keep the temperature 5h, pyrolytic reaction occur, after the reaction was completed, with furnace
It is cooled to room temperature, takes out；
Step 5: annealing, annealing temperature are 500 DEG C, and heating rate is 20 DEG C/min, and atmosphere is argon gas, gas flow rate
In 300CC/min, soaking time is 5 hours.
Step 6: the Chinese prickly ash carbon elder generation alkali cleaning after annealing, rear pickling are finally washed to neutrality, and lye is selected from potassium hydroxide, hydrogen
Sodium oxide molybdena, lithium hydroxide, ammonium hydroxide, acid solution are selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid；The hydroxyl concentration of lye be 0.3mol L,
The hydrogen ion concentration of acid solution be 0.5mol L, wash time be 1 hour, wash temperature be 10 DEG C.
Filtering, obtained product 80 DEG C of dry 12h in an oven, can be obtained the anode material of lithium-ion battery.
Fig. 1 is that the Chinese prickly ash Carbon anode that embodiment 1 obtains is used for filling under 0.1C multiplying power when anode material of lithium-ion battery
Discharge cycles curve；The reversible charging capacity of first circle is 310.1mAh/g, and capacity still maintains as 275.4mAh/g after circulation 100,
Capacity retention ratio is 85%.
Embodiment 2
A method of anode material of lithium-ion battery is prepared using Chinese prickly ash waste material, comprising the following steps:
Step 1: the cooked wild pepper seed of collection cooking first is placed in heating cleaning in acetone and removes surface grease, cleaning
Fluid temperature is 10 DEG C, obtained product 80 DEG C of dry 15h in an oven, to remove moisture removal；
Step 2: to Chinese prickly ash into pickling after the alkali cleaning of passerby elder generation before pre- carbonization, lye is selected from potassium hydroxide, and acid solution is selected from sulfuric acid；
The hydroxyl concentration of lye be 1mol L, the hydrogen ion concentration of acid solution be 1mol L, wash time is 10 hours, wash temperature
It is 90 DEG C.
Step 3: the sample after drying being put into tube furnace, under the protection of nitrogen, with the heating rate of 10 DEG C/min
It is carbonized in advance by room temperature to 200 DEG C, keeps the temperature 0.5h, after the completion, with furnace cooled to room temperature, taken out；
Step 4: sample being put into tube furnace, atmosphere is nitrogen, gas flow rate 5CC/min, with the heating of 1 DEG C/min
Rate keeps the temperature 1h by room temperature to 600 DEG C of progress high temperature cabonizations, and pyrolytic reaction occurs and cools to room with the furnace after the reaction was completed
Temperature is taken out；
Step 5: annealing, annealing temperature are 200 DEG C, and heating rate is 1 DEG C/min, and atmosphere is nitrogen, gas flow rate
In 5CC/min, soaking time is 0.5 hour.
Step 6: the Chinese prickly ash carbon elder generation alkali cleaning after annealing, rear pickling are finally washed to neutrality, and lye is selected from potassium hydroxide, acid
Liquid is selected from sulfuric acid；The hydroxyl concentration of lye be 1mol L, the hydrogen ion concentration of acid solution be 1mol L, wash time is 10 small
When, wash temperature is 90 DEG C.
Filtering, obtained product 70 DEG C of dry 10h in an oven, can be obtained the anode material of lithium-ion battery.
Fig. 2 be the obtained Chinese prickly ash Carbon anode of the embodiment of the present invention 2 for sodium-ion battery when first circle under 0.1C multiplying power
Charging and discharging curve；The first circle coulombic efficiency for showing the negative electrode material is 80.4%.
Embodiment 3
A method of anode material of lithium-ion battery is prepared using Chinese prickly ash waste material, comprising the following steps:
Step 1: collection Pericarpium Zanthoxyli first is placed in water heating cleaning, and cleaning liquid temperature is 50 DEG C, and obtained product exists
60 DEG C of dry 12h in baking oven, to remove moisture removal；
Step 2: independent alkali cleaning being carried out to Chinese prickly ash before pre- carbonization, lye is selected from sodium hydroxide；The hydroxyl concentration of lye is
0.3mol L, wash time be 5 hours, wash temperature be 50 DEG C.
Step 3: sample of the step 1 after dry is put into tube furnace, under the protection of argon gas and the gaseous mixture of nitrogen, with
The heating rate of 10 DEG C/min is carbonized in advance by room temperature to 300 DEG C, and heat preservation 2h naturally cools to room with furnace after the completion
Temperature is taken out；
Step 4: by step 2, treated that sample is put into tube furnace, and atmosphere is the gaseous mixture of argon gas and nitrogen, gas stream
Speed is 100CC/min, with the heating rate of 10 DEG C/min by room temperature to 1200 DEG C of progress high temperature cabonizations, keeps the temperature 3h, occurs
Pyrolytic reaction cools to room temperature with the furnace after the reaction was completed, takes out；
Step 5: annealing, annealing temperature are 350 DEG C, and heating rate is 10 DEG C/min, and atmosphere is argon gas and nitrogen
Gaseous mixture, for gas flow rate in 100CC/min, soaking time is 2 hours.
Step 6: the Chinese prickly ash carbon elder generation alkali cleaning after annealing, rear pickling are finally washed to neutrality, and lye is selected from ammonium hydroxide, acid solution choosing
From acetic acid；The hydroxyl concentration of lye be 5mol L, the hydrogen ion concentration of acid solution be 5mol L, wash time is 5 hours, washing
Temperature is 10-90 DEG C.
Fig. 3 be the obtained Chinese prickly ash hard carbon cathode of the embodiment of the present invention 3 for kalium ion battery when in 0.1C, 0.2C, 0.5C,
Charging and discharging curve under 1C, 2C multiplying power；Show that the negative electrode material has good high rate performance as kalium ion battery.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, all those of ordinary skill in the art are completed without departing from the spirit and technical ideas disclosed in the present invention
All equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of preparation method of Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material, it is characterised in that the following steps are included:
Step 1 collects Chinese prickly ash first, washes and dries processing；
Step 2, by treated that Chinese prickly ash is placed in tube furnace under the protection of inert gas is carbonized in advance, high temperature cabonization, with
And annealing；
Chinese prickly ash carbon lye, acid solution, water after step 3, annealing successively wash, and it is negative that Chinese prickly ash hard carbon sodium ions to potassium ions are obtained after drying
Pole material.
2. the preparation method of Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material according to claim 1, it is characterised in that: described
Chinese prickly ash is Pericarpium Zanthoxyli or cooked Chinese prickly ash waste material, including pricklyash hull, wild pepper seed wherein at least one.
3. the preparation method of Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material according to claim 1, it is characterised in that: step 1
Chinese prickly ash is placed in water, ethyl alcohol, methanol, cleaning removes surface grease in one or several kinds of mixed solutions in acetone when middle cleaning,
Cleaning liquid temperature is 10-100 DEG C.
4. the preparation method of Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material according to claim 1, it is characterised in that: step 2
In pickling after independent pickling or independent alkali cleaning or first alkali cleaning carried out to Chinese prickly ash before carbonization in advance, lye be selected from potassium hydroxide,
Sodium hydroxide, lithium hydroxide, ammonium hydroxide, acid solution are selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid；The hydroxyl concentration of lye is 0.3-
1mol L, the hydrogen ion concentration of acid solution be 0.5-3mol L, wash time is 1-10 hour, and wash temperature is 10-90 DEG C.
5. the preparation method of Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material according to claim 1, it is characterised in that: step 2
In the temperature that is carbonized in advance be 200-500 DEG C, atmosphere is the gaseous mixture of argon gas or nitrogen or air or argon gas and nitrogen, heat preservation
Time is 0.5-5 hours.
6. the preparation method of Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material according to claim 1, it is characterised in that: step 2
The temperature of high temperature carbonization is 600-2000 DEG C, and heating rate is 1-20 DEG C/min, atmosphere be argon gas or nitrogen or air or
The gaseous mixture of argon gas and nitrogen, gas flow rate 5-300CC/min, soaking time are 1-5 hours.
7. the preparation method of Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material according to claim 1, it is characterised in that: step 2
When middle annealing, annealing temperature is 200-500 DEG C, and heating rate is 1-20 DEG C/min, and atmosphere is argon gas or nitrogen or sky
The gaseous mixture of gas or argon gas and nitrogen, for gas flow rate in 5-300CC/min, soaking time is 0.5-5 hours.
8. the preparation method of Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material according to claim 1, it is characterised in that: step 3
Chinese prickly ash carbon elder generation alkali cleaning after middle annealing, rear pickling are finally washed to neutrality, and lye is selected from potassium hydroxide, sodium hydroxide, hydroxide
Lithium, ammonium hydroxide, acid solution are selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid；The hydroxyl concentration of lye be 0.3-5mol L, the hydrogen ion of acid solution
Concentration be 0.5-5mol L, wash time be 1-10 hour, wash temperature be 10-90 DEG C.
9. the Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material that preparation method described in claim 1 to 8 any one obtains.
10. the purposes that the obtained Chinese prickly ash hard carbon sodium ions to potassium ions negative electrode material of claim 9 is used for sodium ions to potassium ions battery electrode.
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| CN109678130A (en) * | 2018-12-20 | 2019-04-26 | 电子科技大学 | A kind of hard carbon material for sodium-ion battery cathode and preparation method thereof and related sodium-ion battery |
| CN110571432A (en) * | 2019-08-15 | 2019-12-13 | 合肥国轩高科动力能源有限公司 | element-doped biomass hard carbon negative electrode material for sodium ion battery, preparation method and sodium ion battery |
| CN112225194A (en) * | 2020-09-24 | 2021-01-15 | 中国科学院化学研究所 | Hard carbon material and preparation method and application thereof |
| CN112299391A (en) * | 2020-10-15 | 2021-02-02 | 南京师范大学 | Water chestnut derived oxygen-doped carbon material and preparation method and application thereof |
| CN115259136A (en) * | 2022-08-31 | 2022-11-01 | 哈尔滨工业大学 | Method for preparing biomass-based hard carbon material in large batch by using waste biomass |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112299391A (en) * | 2020-10-15 | 2021-02-02 | 南京师范大学 | Water chestnut derived oxygen-doped carbon material and preparation method and application thereof |
| CN115259136A (en) * | 2022-08-31 | 2022-11-01 | 哈尔滨工业大学 | Method for preparing biomass-based hard carbon material in large batch by using waste biomass |
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