CN109592660A - A kind of hard carbon presoma using carbon containing biological mass shell preparation, hard carbon/graphite composite material and its preparation method and application - Google Patents
A kind of hard carbon presoma using carbon containing biological mass shell preparation, hard carbon/graphite composite material and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of hard carbon presomas prepared using carbon containing biological mass shell, hard carbon/graphite composite material and its preparation method and application.The hard carbon presoma is made by the steps to obtain: S1: carbon containing biological mass shell powder being added in oxytropism solution, microwave hydrothermal reaction, washing, up to hard carbon presoma after removal of impurities are carried out under 100 ~ 180 DEG C of closed environments.The present invention is under microwave condition handled biomass using acid solution, and hard carbon presoma is obtained in the case where not destroying the natural structure of material, and first charge discharge efficiency obtains larger raising.The excellent properties of graphite and hard carbon material are had both using hard carbon/graphite composite material that the hard carbon precursor preparation obtains, and have first charge discharge efficiency high, the advantages that cycle performance is excellent, and specific capacity is high, good rate capability under big multiplying power；Preparation method simple process, manipulation is convenient, and low in raw material price, abundance, equipment investment is small, and energy consumption is low, is conducive to be mass produced, and practicability is high.
Description
Technical field
The invention belongs to lithium ion battery negative material fields, and in particular to a kind of to utilize the hard of carbon containing biological mass shell preparation
Carbon matrix precursor, hard carbon/graphite composite material and its preparation method and application.
Background technique
Lithium ion battery has excellent performance, as operating voltage is high, specific energy height, good cycle, memory-less effect
The advantages that.Wherein the negative electrode material of lithium ion battery is the key factor for influencing battery performance again, especially influences following for battery
The performances such as ring, multiplying power.The negative electrode material of lithium ion battery is mainly graphite (modified natural graphite, artificial graphite), and reason is
Its good conductivity, reversible specific capacity are high, but the structural stability of graphite material is poor, the poor compatibility with electrolyte, and lithium from
Diffusion velocity of the son in its ordered lamellar structure is slow, causes the material cannot the charge and discharge of big multiplying power ground.Meanwhile with portable
The demand of miniaturization of electronic products development and lithium ion battery in aviation, military affairs and automobile industry is increasingly vigorous, the appearance of battery
Amount and energy density also urgently increase substantially.Therefore, people express the negative electrode material of Novel high-specific capacity flexible, long circulation life
Great expectations.
Hard carbon belongs to ungraphitised carbon, and structure feature may be summarized to be shortrange order and longrange disorder, mainly think structure
Including turbostratic graphite nanocrystal arbitrarily disperse, small, curved graphite flake layer, and be present in first two structure type it
In empty structure.Hard carbon is the pyrolytic carbon of high molecular polymer, is difficult to be graphitized, it has interlaced stratiform knot
Structure substantially increases the speed of charge and discharge so that lithium ion can be embedded in and deviate from from all angles, has hard carbon excellent
Different multiplying power and cycle performance and cryogenic property.But it is low with reversible capacity, first charge discharge efficiency is low low with discharge voltage etc.
Disadvantage.The common source of hard carbon material is divided into fossil fuel residue and agriculture/forestry products waste/by-product etc., wherein latter
Kind of source belongs to biomass source, at present with environment friendly, it is at low cost the features such as, become prepare hard carbon material concern it is burnt
Point.
Therefore, a kind of first charge discharge efficiency height, the negative electrode material tool of high rate performance, cycle performance and low temperature performance excellent are developed
There are important research significance and application value.
Summary of the invention
It is an object of the invention to overcome graphite stable in the prior art and high rate performance bad, the reversible appearance of hard carbon material
Low, the first charge discharge efficiency low defect and deficiency low with discharge voltage are measured, before a kind of hard carbon using carbon containing biological mass shell preparation is provided
Drive body.The present invention is under microwave condition handled biomass using acid solution, is not destroying the natural structure of material
In the case of obtain hard carbon presoma, first charge discharge efficiency is improved.Hard carbon/graphite composite material is prepared into excellent
Multiplying power and cycle performance.
Another object of the present invention is to provide application of the above-mentioned hard carbon presoma in preparation negative electrode material.
Another object of the present invention is to provide a kind of hard carbon/graphite composite materials.
Another object of the present invention is to provide above-mentioned hard carbon/graphite composite materials in preparing negative electrode of lithium ion battery
Using.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of hard carbon presoma using carbon containing biological mass shell preparation, the hard carbon presoma are made by the steps to obtain:
S1: carbon containing biological mass shell powder is added in oxytropism solution, it is anti-that microwave hydrothermal is carried out under 100 ~ 180 DEG C of closed environments
It answers, washs, up to hard carbon presoma after removal of impurities.
In the prior art, generally biomass is handled using alkali, but the processing mode has reaction only anti-on surface
The shortcomings that answering and being easily destroyed the natural structure and low equal first charge discharge efficiency of biological material.The present inventor is by repeatedly tasting
Examination discovery, under microwave condition handles biomass using acid solution, the first charge discharge efficiency of material can be made to be improved；Its
In, acid solution can not destroy the natural structure of material, and microwave condition can make that reaction temperature is uniform, the reaction time is short, heating effect
Rate height and energy-efficient advantage, finally obtained hard carbon presoma first charge discharge efficiency are high；Using the hard carbon presoma and graphite into
The compound obtained hard carbon/graphite composite material of row has excellent multiplying power and cycle performance.
More specifically, the step S1 the following steps are included:
S11: biological mass shell is grinding to obtain biological mass shell powder, and biological mass shell powder is evenly dispersed in an acidic solution,
Obtain solution A；
S12: solution A is reacted through microwave hydrothermal, obtains pretreated carbon containing powdered biomass；
S13: the pretreated carbon containing powdered biomass of step S12 is washed, and the washing is to clean through aqueous slkali, then spend
Ion water washing obtains hard carbon presoma.
Acid solution conventional in the art is used equally for the present invention, and concentration is also normal concentration.
Preferably, the acid solution is one of sulfuric acid solution, hydrochloric acid solution, nitric acid solution or phosphoric acid solution or several
Kind.
Preferably, the concentration of the acid solution is 1 ~ 5 mol/L.
Preferably, the mass ratio of the acid in the acid solution and carbon containing biological mass shell powder is 3 ~ 7:10.
Preferably, the time of the microwave hydrothermal reaction is 10 ~ 120 min.
Preferably, the power of the microwave is 0.4 ~ 1 kW.
Preferably, the temperature of the microwave hydrothermal reaction is 150 DEG C, time 30min.
Carbon containing biological mass shell powder in the present invention is the powdered form of conventional biomass.
The powder for the carbon containing biological mass shell that carbon containing biology mass shell powder described in step S1 can routinely be used using this field
End, it is preferred to use one or more of walnut shell powder, coconut shell powder or pistachio shell powder.
Preferably, the microwave hydrothermal reaction is carried out using microwave hydrothermal reaction kettle, in the microwave hydrothermal reaction kettle
The compactedness of solution is 80%.
Preferably, the washing is to clean through enough aqueous slkalis, then be washed with deionized to neutrality, and it is extra to remove
Foreign ion obtains hard carbon presoma.
It is further preferable that the aqueous slkali is sodium hydroxide solution.
Application of the above-mentioned hard carbon presoma in preparation negative electrode material is also within the scope of the present invention.
A kind of hard carbon/graphite composite material, is prepared by the following procedure step and is prepared:
S2: by graphite dispersion in dispersing agent, any hard carbon presoma in addition is stirred, dry, under inert atmosphere
500 ~ 700 DEG C of pre- 1 ~ 5h of carbonization treatment obtain pre- carbonization hard carbon/graphite composite material presoma；The graphite and hard carbon forerunner
The mass ratio of body is 0.1 ~ 1:1；
S3: will pre- carbonization hard carbon/graphite composite material presoma under the inert atmosphere of flowing 800 ~ 1300 DEG C of carbonization treatments 2 ~
8 h to get arrive hard carbon/graphite composite material.
Both graphite is dispersed using dispersing agent, then is mixed with the hard carbon presoma with excellent properties, may make
It mixes more uniformly, effectively improves the high rate performance of finally obtained hard carbon/graphite composite material.
Preparation method simple process provided by the invention, manipulation is convenient, raw materials used cheap, abundance, equipment
Put into small, energy consumption is low, is conducive to be mass produced, have excellent performance, and practicability is high；The hard carbon graphite being prepared is compound
Material has both the excellent properties of graphite and hard carbon material, has first charge discharge efficiency high, and cycle performance is excellent, and specific capacity is high, big multiplying power
Under good rate capability the advantages that.
More specifically, step S2 the following steps are included:
S21: dispersing agent is added in deionized water and is dissolved, graphite is added, obtains solution B after stirring；
S22: hard carbon presoma of the present invention is added in solution B, and stirring obtains solution C, dry；
S23: the presoma that step S22 is obtained pre- carbonization treatment under inert atmosphere is cooled to room after pre- carbonization treatment
Temperature obtains pre- carbonization hard carbon/graphite composite material presoma.
Conventionally used for realizing that the dispersing agent of graphite fine dispersion is used equally in the present invention in this field.
Preferably, the dispersing agent is one or both of OP-10 or PVP.
Preferably, the mass ratio of the graphite and hard carbon presoma is 0.1:1.
Preferably, the temperature of the pre- carbonization treatment is 550 DEG C, time 2h.
Preferably, the heating rate of the pre- carbonization treatment is 1 ~ 20 DEG C/min.
Preferably, the temperature of the carbonization treatment is 1000 DEG C, time 2h.
Preferably, the heating rate of carbonization treatment described in S3 is 1 ~ 20 DEG C/min.
Preferably, the inert atmosphere is nitrogen atmosphere.
Above-mentioned hard carbon/graphite composite material is preparing the application in negative electrode of lithium ion battery also in protection scope of the present invention
It is interior.
Compared with prior art, the invention has the following beneficial effects:
The present invention is under microwave condition handled carbon containing biomass using acid solution, in the natural structure for not destroying material
In the case where obtain hard carbon presoma, first charge discharge efficiency obtains larger raising.Hard carbon/the stone obtained using the hard carbon precursor preparation
Black composite material has both the excellent properties of graphite and hard carbon material, has first charge discharge efficiency high, and cycle performance is excellent, and specific capacity is high,
The advantages that good rate capability under big multiplying power.
Invention further provides the preferred process of preparing of hard carbon/graphite composite material, the preparation process sides
Method simple process, manipulation is convenient, and raw materials used cheap, abundance, equipment investment is small, and energy consumption is low, is conducive to big
Large-scale production is had excellent performance, and practicability is high.
Detailed description of the invention
Fig. 1 is the XRD diagram of carbon containing biological mass shell hard carbon/graphite composite material prepared by embodiment 1
Fig. 2 is the grain size distribution of carbon containing biological mass shell hard carbon/graphite composite material prepared by embodiment 1；
Fig. 3 is the button electricity curve of carbon containing biological mass shell hard carbon/graphite composite material prepared by embodiment 1.
Specific embodiment
Below with reference to embodiment, the present invention is further explained.These embodiments are merely to illustrate the present invention rather than limitation
The scope of the present invention.Test method without specific conditions in lower example embodiment usually according to this field normal condition or is pressed
The condition suggested according to manufacturer；Used raw material, reagent etc., unless otherwise specified, being can be from the business such as conventional market
The raw materials and reagents that approach obtains.The variation for any unsubstantiality that those skilled in the art is done on the basis of the present invention
And replacement belongs to scope of the present invention.
Button cell test method used in the present invention are as follows: respectively by embodiment 1 ~ 4, comparative example 1 ~ 2 and graphite cathode material
Cell negative electrode material obtained is uniformly mixed with conductive agent, SBR and CMC according to 95.5:1.5:1.5:1.5, is applied on copper foil, very
It is used as cathode after sky is dry, is to electrode with lithium metal, electrolyte uses the ethylene carbonate (EC) and carbonic acid two of 1M LiPF6
Methyl esters (DMC) is the mixed liquor of 1:1 in mass ratio, and diaphragm is PE/PP/PE composite membrane, is assembled into button cell.With the electricity of 0.2C
Current density carries out charge and discharge, and charging voltage is limited to 0.005-2V.
Embodiment 1
The present embodiment provides a kind of hard carbon/graphite composite materials, the preparation method is as follows:
S11: weighing 20g walnut shell and crushed with pulverizer, obtains mangosteen shell powder, and obtained walnut shell powder is evenly dispersed
It is 3mol/L H in concentration2SO4In (70mL, each embodiment is equal, comparative example is identical with this), solution A is obtained；
S12: solution A is added in microwave hydrothermal reaction kettle, and the power for adjusting microwave is 0.8kW, in 150 DEG C of sealing hydro-thermals
Reaction kettle is cooled to room temperature later by 30min, obtains pretreated carbon containing powdered biomass；
S13: enough sodium hydroxides are added in pretreated carbon containing powdered biomass and are cleaned, then are washed with deionized into
Property, extra foreign ion is removed, hard carbon presoma is obtained；
S21: the OP-10 of 1mL being added in deionized water and is dissolved, graphite is added, and is stirred 30min using high speed agitator, is obtained
To solution B；
S22: hard carbon presoma is added in solution B, and the mass ratio with graphite is 0.1:1, is stirred using high speed agitator
30min obtains solution C, in 80 DEG C of dry 10h；
S23: the obtained presoma of step S22 is transferred in shaft furnace, 550 DEG C of heat treatment 2h under the nitrogen atmosphere of flowing,
It is cooled to room temperature after pre- carburizing reagent, obtains pre- carbonization hard carbon/graphite composite material presoma；
S3: the presoma that is carbonized in advance obtained in step S23 is transferred to tube furnace, under the nitrogen atmosphere of flowing at 1000 DEG C of heat
2h is managed, room temperature is cooled to after carburizing reagent, obtains hard carbon/graphite composite material.
Fig. 1 is hard carbon/graphite composite material XRD diagram, from figure it is found that in the presence of having hard carbon, the diffraction maximum of sample
Intensity can reduce.
Fig. 2 is hard carbon/graphite composite material grain size distribution, from figure it is found that the hard carbon/graphite composite material dispersion
Spend, particle diameter distribution it is uniform；Increase with the average grain diameter (D50) of graphite-phase ratio, composite sample.
Embodiment 2
The present embodiment provides a kind of hard carbon/graphite composite materials, the preparation method is as follows:
S11: weighing 20g walnut shell and crushed with pulverizer, obtains mangosteen shell powder, and obtained mangosteen shell powder is evenly dispersed
It is 1mol/L H in concentration2SO4In, obtain solution A；
S12: solution A is added in microwave hydrothermal reaction kettle, in 100 DEG C of sealing hydro-thermal 120min, is later cooled to reaction kettle
Room temperature obtains pretreated carbon containing powdered biomass；
S13: enough sodium hydroxides are added in pretreated carbon containing powdered biomass and are cleaned, then are washed with deionized into
Property, extra foreign ion is removed, hard carbon presoma is obtained；
S21: the OP-10 of 1mL being added in deionized water and is dissolved, graphite is added, and is stirred 30min using high speed agitator, is obtained
To solution B；
S22: hard carbon presoma is added in solution B, and the mass ratio with graphite is 0.15:1, is stirred using high speed agitator
30min obtains solution C, in 80 DEG C of dry 10h；
S23: the obtained presoma of step S22 is transferred in shaft furnace, 500 DEG C of heat treatment 5h under the nitrogen atmosphere of flowing,
It is cooled to room temperature after pre- carburizing reagent, obtains pre- carbonization hard carbon/graphite composite material presoma；
S3: the presoma that is carbonized in advance obtained in step S23 is transferred to tube furnace, under the nitrogen atmosphere of flowing at 1300 DEG C of heat
2h is managed, room temperature is cooled to after carburizing reagent, obtains hard carbon/graphite composite material.
Embodiment 3
The present embodiment provides a kind of hard carbon/graphite composite materials, the preparation method is as follows:
S11: weighing 20g walnut shell and crushed with pulverizer, obtains mangosteen shell powder, and obtained mangosteen shell powder is evenly dispersed
It is 5mol/L H in concentration2SO4In, obtain solution A；
S12: solution A is added in microwave hydrothermal reaction kettle, in 180 DEG C of sealing hydro-thermal 10min, reaction kettle is cooled to room later
Temperature obtains pretreated carbon containing powdered biomass；
S13: enough sodium hydroxides are added in pretreated carbon containing powdered biomass and are cleaned, then are washed with deionized into
Property, extra foreign ion is removed, hard carbon presoma is obtained；
S21: the OP-10 of 1mL being added in deionized water and is dissolved, graphite is added, and is stirred 30min using high speed agitator, is obtained
To solution B；
S22: hard carbon presoma is added in solution B, and the mass ratio with graphite is 0.2:1, is stirred using high speed agitator
30min obtains solution C, in 80 DEG C of dry 10h；
S23: the obtained presoma of step S22 is transferred in shaft furnace, 700 DEG C of heat treatment 1h under the nitrogen atmosphere of flowing,
It is cooled to room temperature after pre- carburizing reagent, obtains pre- carbonization hard carbon/graphite composite material presoma；
S3: the presoma that is carbonized in advance obtained in step S23 is transferred to tube furnace, under the nitrogen atmosphere of flowing at 800 DEG C of heat
2h is managed, room temperature is cooled to after carburizing reagent, obtains hard carbon/graphite composite material.
Embodiment 4
The present embodiment provides a kind of hard carbon/graphite composite materials, the preparation method is as follows:
S11: weighing 20g coconut husk and crushed with pulverizer, obtains coconut shell powder, and obtained coconut shell powder is dispersed in concentration
To obtain solution A in 3mol/L phosphoric acid；
S12: solution A is added in microwave hydrothermal reaction kettle, in 150 DEG C of sealing hydro-thermal 30min, reaction kettle is cooled to room later
Temperature obtains pretreated carbon containing powdered biomass；
S13: enough sodium hydroxides are added in pretreated carbon containing powdered biomass and are cleaned, then are washed with deionized into
Property, extra foreign ion is removed, hard carbon presoma is obtained；
S21: the PVP of 0.2g being added in deionized water and is dissolved, graphite is added, and is stirred 30min using high speed agitator, is obtained
Solution B；
S22: hard carbon presoma is added in solution B, and the mass ratio with graphite is 1:1, stirs 30min using high speed agitator,
Solution C is obtained, in 80 DEG C of dry 10h；
S23: the obtained presoma of step S22 is transferred in shaft furnace, 550 DEG C of heat treatment 2h under the nitrogen atmosphere of flowing,
It is cooled to room temperature after pre- carburizing reagent, obtains pre- carbonization hard carbon/graphite composite material presoma；
S3: the presoma that is carbonized in advance obtained in step S23 is transferred to tube furnace, under the nitrogen atmosphere of flowing at 1000 DEG C of heat
2h is managed, room temperature is cooled to after carburizing reagent, obtains hard carbon/graphite composite material.
Comparative example 1
This comparative example provides a kind of hard carbon/graphite composite material, preparation method in addition to step S11 ~ S13 is different from embodiment 1,
Remaining step and condition are consistent with embodiment 1, specific as follows.
S11: weighing 20g walnut shell and crushed with pulverizer, obtains walnut shell powder, and obtained walnut shell powder is uniform
Being dispersed in concentration is to obtain solution A in 3mol/L NaOH；
S12: solution A is added in microwave hydrothermal reaction kettle, in 150 DEG C of sealing hydro-thermal 30min, reaction kettle is cooled to room later
Temperature obtains pretreated carbon containing powdered biomass；
S13: enough sulfuric acid solutions are added in pretreated carbon containing powdered biomass and are cleaned, then are washed with deionized into
Property, extra foreign ion is removed, hard carbon presoma is obtained；
Step S21 ~ S23 is consistent with 1 step S21 ~ S23 of embodiment；Step S3 is consistent with 1 step S3 of embodiment.
Comparative example 2
This comparative example provides a kind of hard carbon/graphite composite material, removes in step S12 in preparation method and solution A is added commonly
Other than hydrothermal reaction kettle reaction, remaining step and condition are consistent with embodiment 1.
Comparative example 3
Hard carbon presoma in embodiment 1 is mixed with graphite, is ground；Or mix graphite, hard carbon presoma with water, it stirs
It mixes；It cannot achieve the more uniform mixing of the two, hard carbon/graphite composite material can not be prepared.
The electrochemical property test result of each embodiment, comparative example and graphite material such as table 1.
The electrochemical property test result of 1 embodiment of table, comparative example and graphite material
As can be seen from the above test results that using hard carbon/graphite composite material prepared by the present invention as negative electrode of lithium ion battery material
Battery made of expecting, compared to pure graphite cathode material, the good rate capability with good specific capacity under high, big multiplying power is (such as
Fig. 3).According to the result of comparative example 1 ~ 3 and embodiment it is found that compared with alkaline solution processing, obtained after acid solution processing
Hard carbon/graphite composite material has higher first charge-discharge efficiency and excellent high rate performance；Compared with hydro-thermal reaction, microwave
After hydro-thermal reaction processing obtained hard carbon/graphite composite material have good dispersion degree, particle diameter distribution uniformly, the spy of good rate capability
Point.
Those of ordinary skill in the art will understand that embodiment here be to help reader understand it is of the invention
Principle, it should be understood that protection scope of the present invention is not limited to such specific embodiments and embodiments.This field it is common
Technical staff disclosed the technical disclosures can make the various various other tools for not departing from essence of the invention according to the present invention
Body variations and combinations, these variations and combinations are still within the scope of the present invention.
Claims (10)
1. a kind of hard carbon presoma using carbon containing biological mass shell preparation, which is characterized in that the hard carbon presoma passes through as follows
Step is prepared:
S1: carbon containing biological mass shell powder is added in oxytropism solution, it is anti-that microwave hydrothermal is carried out under 100 ~ 180 DEG C of closed environments
It answers, washs, up to hard carbon presoma after removal of impurities.
2. hard carbon presoma according to claim 1, which is characterized in that the time of the microwave hydrothermal reaction is 10 ~ 120
min。
3. hard carbon presoma according to claim 1, which is characterized in that acid solution described in S1 is sulfuric acid solution, hydrochloric acid
One or more of solution, nitric acid solution or phosphoric acid solution；The concentration of the acid solution is 1 ~ 5 mol/L.
4. hard carbon presoma according to claim 1, which is characterized in that the power of microwave described in S1 is 0.4 ~ 1kW.
5. hard carbon presoma according to claim 1, which is characterized in that carbon containing biology mass shell powder is walnut shell described in S1
One or more of powder, coconut shell powder or pistachio shell powder.
6. application of any hard carbon presoma of claim 1 ~ 5 in preparation negative electrode material.
7. a kind of hard carbon/graphite composite material, which is characterized in that step is prepared by the following procedure and is prepared:
S2: by graphite dispersion in dispersing agent, being added any hard carbon presoma of claim 1 ~ 5, stir, dry, in lazy
500 ~ 700 DEG C of pre- 1 ~ 5h of carbonization treatment under property atmosphere, obtain pre- carbonization hard carbon/graphite composite material presoma；The graphite and
The mass ratio of hard carbon presoma is 0.1 ~ 1:1；
S3: by pre- carbonization hard carbon/graphite composite material presoma 800 ~ 1300 DEG C of 2 ~ 8 h of carbonization under the inert atmosphere of flowing,
Obtain hard carbon/graphite composite material.
8. hard carbon/graphite composite material according to claim 7, which is characterized in that dispersing agent described in S2 be OP-10 or
One or both of PVP.
9. hard carbon/graphite composite material according to claim 7, which is characterized in that the temperature being carbonized in advance described in S2 is 550
DEG C, time 2h；The temperature of carbonization described in S3 is 1000 DEG C, time 2h.
10. any hard carbon/graphite composite material of claim 7 ~ 9 is preparing the application in negative electrode of lithium ion battery.
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| CN110627037A (en) * | 2019-06-26 | 2019-12-31 | 陕西科技大学 | Preparation method of nitrogen-doped biomass porous carbon nano electrode material |
| CN111091976A (en) * | 2019-12-30 | 2020-05-01 | 青岛科技大学 | Biomass/graphene oxide carbon composite material for electrode material and preparation method thereof |
| CN112678797A (en) * | 2020-12-23 | 2021-04-20 | 浙江阿佩克斯能源科技有限公司 | Rapid preparation method of hard carbon material |
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| 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 |
| CN113307248A (en) * | 2021-07-07 | 2021-08-27 | 福建省鑫森炭业股份有限公司 | Electrode material prepared from cheap biomass material and difficult to graphitize and preparation method thereof |
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| CN113903896B (en) * | 2021-09-28 | 2023-09-12 | 上海飞鸿创联新能源发展有限公司 | Secondary particle hard carbon composite material and preparation method and application thereof |
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| CN114864934A (en) * | 2022-04-11 | 2022-08-05 | 温州大学碳中和技术创新研究院 | Preparation method and application of hazelnut shell hard carbon material for sodium ion battery cathode |
| CN115036473A (en) * | 2022-05-19 | 2022-09-09 | 福州大学 | Hard carbon precursor and doped phase-based sodium ion battery negative electrode material and preparation method thereof |
| CN115321516A (en) * | 2022-09-13 | 2022-11-11 | 惠州亿纬锂能股份有限公司 | Biomass-based hard carbon material, preparation method thereof and lithium ion battery |
| CN116477623A (en) * | 2023-04-27 | 2023-07-25 | 哈尔滨工业大学 | Preparation method of nut shell derived porous carbon material and application of nut shell derived porous carbon material in lithium ion battery |
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