CN109921018A - The preparation method of sodium-ion battery high capacity biomass hard charcoal negative electrode material - Google Patents
The preparation method of sodium-ion battery high capacity biomass hard charcoal negative electrode material Download PDFInfo
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Abstract
The present invention relates to technical field of secondary batteries, the preparation method of specifically a kind of sodium-ion battery high capacity biomass hard charcoal negative electrode material, which is characterized in that use following processing step: biomass material being crushed and screened to obtain presoma powder；Add dehydrating agent be uniformly mixed obtain mixture and carry out dehydrating and curing reaction；Biomass presoma after solidification is mixed with modifying agent, and carries out liquid phase mixing by dispersing agent of water, is then dried, obtains modified biomass presoma；Pre- carbonization treatment, carbonization treatment are successively carried out again.The present invention is compared with the existing technology, use starch for raw material, cured processing, effectively avoids the problem that starch high-temperature molten and be gelatinized, starch granules after solidification doped moditied processing again, hard charcoal surface chemistry environment and internal structure are changed, the chemical property of biomass hard charcoal negative electrode material is effectively increased；It is handled using curing reaction and also significantly increases hard charcoal yield.
Description
Technical field
The present invention relates to technical field of secondary batteries, specifically a kind of sodium-ion battery high capacity biomass hard charcoal
The preparation method of negative electrode material.
Background technique
With society development and global energy requirements continuous improvement, fossil energy consume brought by scarcity of resources and
Caused environmental problem becomes increasingly conspicuous.Obviously, from society angle of sustainable development in terms of, Devoting Major Efforts To Developing and utilize renewable energy
Source, gradually getting rid of the mankind seems particularly necessary to the dependence of fossil energy.However, renewable energy is mating using needing to develop
Energy storage facility guarantee the stability of electricity consumption.And current secondary cell technology, due to have flexibly, efficiently and
The advantages that without territory restriction is the current most possible technical solution for being applied to large-scale energy storage device.
At present in secondary cell technology, lithium ion battery development is more mature, using also very extensive.But by the limit of lithium resource
System can not support the development of the following extensive accumulation power supply.And the sodium element of same main group is in lithium, the two is chemically
Matter is similar, and also relatively, and sodium is resourceful for electrode potential, refines at low cost, develops sodium-ion battery technology and has become
For the hot spot of current energy storage field research.
It seeks high capacity and the excellent storage sodium negative electrode material of cycle performance is the key that develop sodium-ion battery of new generation.Mesh
It is preceding relatively fewer for embedding sodium negative electrode material research, mainly it is limited to the graphite material interlamellar spacing with good removal lithium embedded performance
It is smaller, it is unable to satisfy being effectively embedded into and deviating from for larger ionic radius sodium ion.Therefore, it to realize reversible sodium ion insertion and take off
Out, it is crucial that preparation, which has the Carbon Materials of larger interlamellar spacing,.
Hard carbon material have underdeveloped graphite network plane, crystallite width La is smaller, interlamellar spacing (d002) greatly so that hard charcoal
It is suitable as embedding sodium material, while the more pore structure of hard charcoal also provides good place for the storage of sodium, has higher
Embedding sodium capacity, and have good circulation and high rate performance.According to the difference of raw material, hard charcoal can be divided into biomass hard charcoal
(such as carbohydrate, coconut husk), minerals hard charcoal (such as coal tar, petroleum residual oil) and synthetic polymer hard charcoal (such as phenolic resin, ring
Oxygen resin etc.).Wherein, biomass hard charcoal causes to grind because having many advantages, such as that raw material sources are extensive, low in cost and renewable
The extensive concern for the person of studying carefully.Starch base hard charcoal microballoon is mounted to expanded graphite by the Chinese patent of Publication No. CN102364727
In gap, using expanded graphite as solid space conductive network, the electronic conduction ability of hard charcoal is improved, the composite material of formation exists
Discharge capacity is 440-530mAh/g when 0.1C, and first charge discharge efficiency is 77~85%, but its process is cumbersome, higher cost.
The Chinese patent of Publication No. CN105633380A is made from starch, the carbon after amylase, carbohydrase, dehydration catalyst effect
Change obtains the porous hard carbon material of starch base.Compared with without enzyme starch, the porous hard charcoal 0.1C of enzymeization stores up lithium reversible capacity for the first time
454mAh/g is increased to by 305mAh/g, although coulombic efficiency is improved by 42.8% to 66.6%, head effect level for the first time
It is still lower, and its process treatment process is long, stability is difficult to ensure, is not suitable for large-scale production.
Summary of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, equally use biomass for raw material, provide a kind of with miscellaneous
The pyrolysis biomass hard charcoal of element doping, this biomass hard charcoal can adjust charcoal interlamellar spacing and changeization due to miscellaneous element doping
Environment is learned, the insertion and abjection of sodium ion are suitble to when for sodium-ion battery, prepares one by technique simple to operation
Comprehensive performance preferably hard charcoal negative electrode material of the kind particularly suitable as the negative electrode material of sodium ion secondary battery, reduces biology
The production cost of matter hard charcoal.
To achieve the above object, a kind of preparation side of sodium-ion battery high capacity biomass hard charcoal negative electrode material is designed
Method, which is characterized in that use following processing step:
(1), it prepares presoma powder: biomass material being crushed and screened to 2~50 μm, presoma powder is obtained；It is described
Biomass material be starchy material；
(2), dehydrating and curing: in presoma powder be added dehydrating agent be uniformly mixed obtains mixture, with 100~250 DEG C into
Row dehydrating and curing reacts 4-8 hours；The mass ratio of the presoma powder and dehydrating agent is 1: 0.05-0.25；The dehydrating agent
For a kind or 2 kinds in ammonium chloride, ammonium persulfate, the concentrated sulfuric acid, nitric acid, hydrogen peroxide；
(3), prepare modified biomass presoma: by after solidification biomass presoma and modifying agent be in mass ratio 1:
0.05-0.25 mixing, and liquid phase mixing is carried out by dispersing agent of water, it is then dried, obtains modified biomass forerunner
Body；The modifying agent is phosphoric acid, phosphorus pentoxide, boric acid, a kind or 2 kinds in boron oxide；Before biomass after the solidification
Drive body: mass ratio≤1 of dispersing agent；
(4), pre- carbonization treatment: under inert gas protection by gained modified biomass presoma, with 600~800 DEG C into
Row pre- carbonization 1-3 hours, is then down to room temperature and crushes and screens to obtain 1~50 μm of powder of volume average particle size；
(5), carbonization treatment: gained powder carries out carbonization 1-6 hours, drop under inert gas protection, with 900~1200 DEG C
It is sieved to room temperature to get high capacity biomass hard charcoal negative electrode material；The high capacity biomass hard charcoal is not advising for surface compact
Then blocky fine particle, average particle size are 1~50 μm, and real density is 1.4~2.1g/cm3, tap density be 0.5~
1.0g/cm3, specific surface area is 1~100m2/ g, crystal face interlamellar spacing D002 are 0.35-0.39nm.
The starchy material is a kind in rice starch, cornstarch, potato starch, wheaten starch and sweet potato starch
Or 2 kinds.
The crushing of the biomass material uses any one of ball milling, mechanical crushing, air-flow crushing mode；It is preferred that using
It is mechanically pulverized.
Crushing in the pre- carbonization treatment is the broken or ball milling that is milled using airflow milling crushing, the mechanical broken, fluidized bed that is milled
Processing.Particularly preferably handled using air-flow crushing
The dehydrating and curing reaction is carried out in shaft furnace or drying box.
Mixing in the dehydrating and curing is in the stirring with polytetrafluoroethyllining lining that revolving speed is 500~1000r/min
At least 30min is mixed in batch mixer.
The liquid phase is mixed into the high-speed stirred mixing with polytetrafluoroethyllining lining that revolving speed is 1000~2500r/min
At least 30min is mixed in machine.
The drying process prepared in modified biomass presoma is to be dried extremely with 100-150 DEG C in a vacuum drying oven
Water removal completely.
The pre- carbonization treatment is carried out in shaft furnace；
The charing process carries out in atmosphere furnace, batch-type furnace or shaft furnace.Particularly preferably use atmosphere furnace.
The inert gas is nitrogen, helium, a kind or at least two kinds of in argon gas.
Screening in the pre- carbonization treatment was 60~800 the polished standard screen nets.
The present invention compared with the existing technology, has following technical advantage:
Use starch for raw material, cured processing effectively avoids the problem that starch high-temperature molten and is gelatinized, the starch after solidification
Particle doped moditied processing again, changes hard charcoal surface chemistry environment and internal structure, and it is negative to effectively increase biomass hard charcoal
The chemical property of pole material；
It is handled using curing reaction and also significantly increases hard charcoal yield；
The hard charcoal negative electrode material of preparation has reversible storage sodium capacity height, excellent cycle performance and again for sodium-ion battery
Rate performance, is with a wide range of applications；
Preparation method is simple, and raw material is cheap and easy to get, and preparation condition is mildly controllable, and prepared hard charcoal negative electrode material has good
Good pattern and aperture structure, it is suitable for scale production.
Specific embodiment
The present invention is further described now in conjunction with embodiment.
The heating rate of heretofore described pre- carbonization treatment is preferably 0.5~20 DEG C/min；The heating speed of carbonization treatment
Rate is preferably 0.5~20 DEG C/min.
Embodiment 1
1, the broken rice starch for being sieved to volume average particle size and being 10 μm of 1000g is taken；
2, rice starch feeds intake the mixing in stir mixing machine and under 1000r/min revolving speed together with 150g ammonium chloride
10min obtains mixture；Gained mixture is set after being solidified in air dry oven with 150 DEG C of dehydrating and curing reaction 6h
Rice starch presoma；
3, deionized water and 100g phosphoric acid are added in rice starch presoma after hardening, in high-speed stirred batch mixer
Gained solidfied material is prepared into the slurry that solid content is 50%, then is removed water with 150 DEG C of dryings to complete in air dry oven, it is cold
But modified rice starch presoma is obtained afterwards；
4, modified rice starch presoma is fitted into shaft furnace again and is warming up under nitrogen protection with 2 DEG C/min
600 DEG C of pre- carbonization 1h are cooled to after room temperature discharging and adjust partial size using air-flow crushing and obtain pre- carbonized stock to 9 μm；
5, it is reloaded into atmosphere furnace and 1200 DEG C of carbonization 2h is warming up to 2 DEG C/min under nitrogen protection, be cooled to room temperature and go out
Material sieving is to get biomass hard charcoal negative electrode material.
Embodiment 2
1, the broken rice starch for being sieved to volume average particle size and being 10 μm of 1000g is taken；
2, rice starch feeds intake the mixing in stir mixing machine and under 1000r/min revolving speed together with 200g ammonium chloride
10min obtains mixture；Before gained mixture is reacted the rice starch after 6h is solidified in air dry oven with 150 DEG C
Drive body；
3, deionized water and 100g phosphoric acid are added in rice starch presoma after hardening, in high-speed stirred batch mixer
Gained solidfied material is prepared into the slurry that solid content is 50%, then is removed water with 150 DEG C of dryings to complete in air dry oven, it is cold
But modified rice starch presoma is obtained afterwards；
4, modified rice starch presoma is fitted into shaft furnace again and is warming up under nitrogen protection with 2 DEG C/min
600 DEG C of pre- carbonization 1h are cooled to after room temperature discharging and adjust partial size using air-flow crushing and obtain pre- carbonized stock to 9 μm；
5, it is reloaded into atmosphere furnace and 1200 DEG C of carbonization 2h is warming up to 2 DEG C/min under nitrogen protection, be cooled to room temperature and go out
Material sieving is to get biomass hard charcoal negative electrode material.
Embodiment 3
1, the broken rice starch for being sieved to volume average particle size and being 10 μm of 1000g is taken；
2, rice starch feeds intake the mixing in stir mixing machine and under 1000r/min revolving speed together with 150g ammonium chloride
10min obtains mixture；Gained mixture is reacted into the rice starch forerunner after 6h is solidified with 150 DEG C in air dry oven
Body；
3, deionized water and 50g phosphoric acid are added in rice starch presoma after hardening, in high-speed stirred batch mixer
Gained solidfied material is prepared into the slurry that solid content is 50%, then is removed water with 150 DEG C of dryings to complete in air dry oven, it is cold
But modified rice starch presoma is obtained afterwards；
4, modified rice starch presoma is fitted into shaft furnace again and is warming up under nitrogen protection with 2 DEG C/min
600 DEG C of pre- carbonization 1h are cooled to after room temperature discharging and adjust partial size using air-flow crushing and obtain pre- carbonized stock to 9 μm；
5, it is reloaded into atmosphere furnace 2 DEG C/min under nitrogen protection and is warming up to 1200 DEG C of carbonization 2h, be cooled to room temperature discharging
Sieving is to get biomass hard charcoal negative electrode material.
Embodiment 4
1,1000g is taken to be crushed to the rice starch that volume average particle size is 15 μm；
2, rice starch feeds intake the mixing in stir mixing machine and under 1000r/min revolving speed together with 150g ammonium chloride
10min obtains mixture；Before gained mixture is reacted the rice starch after 6h is solidified in air dry oven with 150 DEG C
Drive body；
3, deionized water and 100g phosphoric acid are added in rice starch presoma after hardening, in high-speed stirred batch mixer
Gained solidfied material is prepared into the slurry that solid content is 50%, then is removed water with 150 DEG C of dryings to complete in air dry oven, it is cold
But modified rice starch presoma is obtained afterwards；
4, modified rice starch presoma is fitted into shaft furnace again and is warming up under nitrogen protection with 2 DEG C/min
600 DEG C of pre- carbonization 1h are cooled to after room temperature discharging and adjust partial size using air-flow crushing and obtain pre- carbonized stock to 9 μm；
5, it is reloaded into atmosphere furnace 2 DEG C/min under nitrogen protection and is warming up to 1200 DEG C of carbonization 2h, be cooled to room temperature discharging
Sieving is to get biomass hard charcoal negative electrode material.
Embodiment 5
1, the broken cornstarch for being sieved to volume average particle size and being 10 μm of 1000g is taken；
2, cornstarch feeds intake the mixing in stir mixing machine and under 1000r/min revolving speed together with 150g ammonium chloride
10min obtains mixture；Before gained mixture is reacted the cornstarch after 6h is solidified in air dry oven with 150 DEG C
Drive body；
3, deionized water and 100g phosphoric acid are added in cornstarch presoma after hardening, in high-speed stirred batch mixer
Gained solidfied material is prepared into the slurry that solid content is 50%, then is removed water with 150 DEG C of dryings to complete in air dry oven, it is cold
But modified cornstarch presoma is obtained afterwards；
4, modified cornstarch presoma is fitted into shaft furnace again and 2 DEG C/min is warming up to 600 under nitrogen protection
DEG C pre- carbonization 1h is cooled to after room temperature discharging and adjusts partial size using air-flow crushing and obtain pre- carbonized stock to 9 μm；
5, it is reloaded into atmosphere furnace and 1200 DEG C of carbonization 2h is warming up to 2 DEG C/min under nitrogen protection, be cooled to room temperature and go out
Material sieving is to get biomass hard charcoal negative electrode material.
Embodiment 6
1, the broken wheaten starch for being sieved to volume average particle size and being 10 μm of 1000g is taken；
2, wheaten starch feeds intake the mixing in stir mixing machine and under 1000r/min revolving speed together with 150g ammonium chloride
10min obtains mixture；Before gained mixture is reacted the wheaten starch after 6h is solidified in air dry oven with 150 DEG C
Drive body；
3, deionized water and 100g phosphoric acid are added in wheaten starch presoma after hardening, in high-speed stirred batch mixer
Gained solidfied material is prepared into the slurry that solid content is 50%, then is removed water with 150 DEG C of dryings to complete in air dry oven, it is cold
But modified wheaten starch presoma is obtained afterwards；
4, modified wheaten starch presoma is fitted into shaft furnace again and is warming up under nitrogen protection with 2 DEG C/min
600 DEG C of pre- carbonization 1h are cooled to after room temperature discharging and adjust partial size using air-flow crushing and obtain pre- carbonized stock to 9 μm；
5, it is reloaded into atmosphere furnace and 1200 DEG C of carbonization 2h is warming up to 2 DEG C/min under nitrogen protection, be cooled to room temperature and go out
Material sieving is to get biomass hard charcoal negative electrode material.
Comparative example 1
1, the rice starch that 1000g volume average particle size is 10 μm is placed directly within 150 DEG C of air dry ovens and reacts 6h；
2, deionized water and 100g phosphoric acid is added in gained material, is prepared into gained solidfied material admittedly in high-speed stirred batch mixer
The slurry that content is 50% is dried to complete water removal in 150 DEG C of air dry ovens, obtains modified rice starch after cooling
Modifier；
3, it is loaded into again in shaft furnace and 2 DEG C/min is warming up to 600 DEG C of pre- carbonization 1h under nitrogen protection, be cooled to room
Partial size is adjusted using air-flow crushing after temperature discharging and obtains pre- carbonized stock to 9 μm；
4, it is reloaded into atmosphere furnace 2 DEG C/min under nitrogen protection and is warming up to 1200 DEG C of carbonization 2h, be cooled to room temperature discharging
Sieving is to get biomass hard charcoal negative electrode material.
Comparative example 2
1, the wheaten starch that 1000g volume average particle size is 10 μm is fed intake together with 150g ammonium chloride in stir mixing machine
In and under 1000r/min revolving speed mixing 10min obtains mixture；
2, gained mixture is placed in 150 DEG C of air dry oven reaction 6h and obtains rice starch solidfied material；
3, it is then loaded into shaft furnace and 2 DEG C/min is warming up to 600 DEG C of pre- carbonization 1h under nitrogen protection, be cooled to
Partial size is adjusted using air-flow crushing after room temperature discharging and obtains pre- carbonized stock to 9 μm；
4, it is reloaded into atmosphere furnace 2 DEG C/min under nitrogen protection and is warming up to 1200 DEG C of carbonization 2h, be cooled to room temperature discharging
Sieving is to get biomass hard charcoal negative electrode material.
To biomass hard charcoal negative electrode material obtained in Examples 1 to 6 and comparative example 1~2 carry out respectively partial size,
As a result the test of real density, tap density and specific surface area is listed in table 1.Instrument title used in testing and model are as follows: grain
Diameter: Malvern laser particle size analyzer MS2000；Real density: the full-automatic real density analysis of U.S.'s health tower UltraPYC 1200e type
Instrument；Tap density: tap density tester FZS4-4B；Specific surface area: health tower specific surface area measuring instrument NOVA2000e.
Table 1
Using half-cell test method to the biomass hard charcoal negative electrode material in Examples 1 to 6 and comparative example 1~2 into
Row charge-discharge property, cycle performance test and high rate performance test, are as a result listed in table 1.Prepared biomass hard charcoal material
Material is negative electrode active material, with vinylidene (PVDF) (being dissolved in N methyl pyrrolidone), conductive black according to mass ratio 80:
10: 10 ratio is uniformly mixed, and is applied as electrode film, is put 120 DEG C of dry 12h in a vacuum drying oven, through roll-in, be punched to obtain the final product
Hard carbon cathode pole piece.Made using metallic sodium piece to electrode, 1mol/L NaPF6 (EC-DEC=1: 1) is electrolyte, by above-mentioned institute
It obtains hard charcoal cathode pole piece and is assembled into 2430 button-shaped electricity in the glove box of the argon atmosphere of water, oxygen content less than 0.1ppm
Its chemical property is tested in pond.The test of chemical property carries out on U.S.'s Arbin electrochemical detection system, charging/discharging voltage
Range is 0 to 2.0V (Na+/ Na), test multiplying power be 0.1C, 1C and 10C, test for the first time reversible capacity, for the first time coulombic efficiency and
Cycle performance.The discharge capacity of coulombic efficiency=initial charge capacity/for the first time for the first time.
As shown in Table 1, use rice starch, cornstarch and wheaten starch for raw material, embodiment 1, is implemented embodiment 2
Example 5 and embodiment 6 can obtain the biomass hard charcoal negative electrode material of electrochemical performance:
Reversible capacity is 260mAh/g to the resulting biomass hard charcoal cathode of embodiment 1 for the first time at 0.1C, and coulomb is imitated for the first time
Rate is that capacity retention ratio is 98.2% after 78.2%, 10C/1C capacity retention ratio is 95.5%, 0.1C charge and discharge cycles 100 times.
Reversible capacity is 263mAh/g to the resulting modified hard charcoal cathode of embodiment 2 for the first time at 0.1C, for the first time coulombic efficiency
Capacity retention ratio is 98.7% after being 96.6%, 0.1C charge and discharge cycles 100 times for 78.9%, 10C/1C capacity retention ratio.
Reversible capacity is 258mAh/g to the resulting modified hard charcoal cathode of embodiment 5 for the first time at 0.1C, for the first time coulombic efficiency
Capacity retention ratio is 97.2% after being 96.5%, 0.1C charge and discharge cycles 100 times for 77.1%, 10C/1C capacity retention ratio.
Reversible capacity is 261mAh/g to the resulting modified hard charcoal cathode of embodiment 6 for the first time at 0.1C, for the first time coulombic efficiency
Capacity retention ratio is 96.7% after being 96.6%, 0.1C charge and discharge cycles 100 times for 76.7%, 10C/1C capacity retention ratio.
The above results show that biomass hard charcoal obtained by the present invention has biggish interlamellar spacing and suitable random layer porous structure,
The free deintercalation of the bigger sodium ion of suitable ionic radius.In comparison, the reversible appearance of comparative example 1 and comparative example 2
Amount and for the first time coulombic efficiency are substantially reduced, and show that rice starch can effectively reduce gained through solidification in advance and again modification
Fault of construction in biomass hard charcoal microcosmic point reduces irreversible embedding sodium capacity.Gained biomass hard charcoal negative electrode material is to sodium
Ion shows higher embedding/deintercalation sodium capacity, high rate performance and good cycle performance, is a kind of with larger application potential
Storage sodium negative electrode material.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
Claims (10)
1. a kind of sodium-ion battery preparation method of high capacity biomass hard charcoal negative electrode material, which is characterized in that using as follows
Processing step:
(1), it prepares presoma powder: biomass material being crushed and screened to 2~50 μm, presoma powder is obtained；The life
Raw material of substance is starchy material；
(2), dehydrating and curing: addition dehydrating agent, which is uniformly mixed, in presoma powder obtains mixture, is taken off with 100~250 DEG C
Water cure reacts 4-8 hours；The mass ratio of the presoma powder and dehydrating agent is 1: 0.05-0.25；The dehydrating agent is chlorine
Change ammonium, ammonium persulfate, the concentrated sulfuric acid, nitric acid, a kind or 2 kinds in hydrogen peroxide；
(3), prepare modified biomass presoma: by after solidification biomass presoma and modifying agent be in mass ratio 1: 0.05-
0.25 mixing, and liquid phase mixing is carried out by dispersing agent of water, it is then dried, obtains modified biomass presoma；Institute
Modifying agent is stated as a kind or 2 kinds in phosphoric acid, phosphorus pentoxide, boric acid, boron oxide；Biomass presoma after the solidification:
Mass ratio≤1 of dispersing agent；
(4), it pre- carbonization treatment: under inert gas protection by gained modified biomass presoma, is carried out with 600~800 DEG C pre-
Carbonization 1-3 hours, is then down to room temperature and crushes and screens to obtain 1~50 μm of powder of volume average particle size；
(5), carbonization treatment: gained powder carries out carbonization 1-6 hours under inert gas protection, with 900~1200 DEG C, is down to room
Temperature sieving is to get high capacity biomass hard charcoal negative electrode material；The high capacity biomass hard charcoal is the irregular block of surface compact
Shape fine particle, average particle size are 1~50 μm, and real density is 1.4~2.1g/cm3, tap density is 0.5~1.0g/
cm3, specific surface area is 1~100m2/ g, crystal face interlamellar spacing D002 are 0.35-0.39nm.
2. the sodium-ion battery as described in claim 1 preparation method of high capacity biomass hard charcoal negative electrode material, feature
It is, the starchy material is a kind or 2 in rice starch, cornstarch, potato starch, wheaten starch and sweet potato starch
Kind.
3. the sodium-ion battery as described in claim 1 preparation method of high capacity biomass hard charcoal negative electrode material, feature
It is,
The crushing of the biomass material uses any one of ball milling, mechanical crushing, air-flow crushing mode；
Crushing in the pre- carbonization treatment is the broken or ball-milling treatment that is milled using airflow milling crushing, the mechanical broken, fluidized bed that is milled.
4. the sodium-ion battery as described in claim 1 preparation method of high capacity biomass hard charcoal negative electrode material, feature
It is, the dehydrating and curing reaction is carried out in shaft furnace or drying box.
5. the sodium-ion battery as described in claim 1 preparation method of high capacity biomass hard charcoal negative electrode material, feature
It is, the mixing in the dehydrating and curing is in the stir mixing with polytetrafluoroethyllining lining that revolving speed is 500~1000r/min
At least 30min is mixed in machine.
6. the sodium-ion battery as described in claim 1 preparation method of high capacity biomass hard charcoal negative electrode material, feature
It is, the liquid phase is mixed into the high-speed stirred batch mixer with polytetrafluoroethyllining lining that revolving speed is 1000~2500r/min
Middle mixing at least 30min.
7. the sodium-ion battery as described in claim 1 preparation method of high capacity biomass hard charcoal negative electrode material, feature
It is, the drying process prepared in modified biomass presoma is dry to complete with 100-150 DEG C in a vacuum drying oven
Full water removal.
8. the sodium-ion battery as described in claim 1 preparation method of high capacity biomass hard charcoal negative electrode material, feature
It is,
The pre- carbonization treatment is carried out in shaft furnace；
The charing process carries out in atmosphere furnace, batch-type furnace or shaft furnace.
9. the sodium-ion battery as described in claim 1 preparation method of high capacity biomass hard charcoal negative electrode material, feature
It is, the inert gas is nitrogen, helium, a kind or at least two kinds of in argon gas.
10. the sodium-ion battery as described in claim 1 preparation method of high capacity biomass hard charcoal negative electrode material, feature
It is, the screening in the pre- carbonization treatment was 60~800 the polished standard screen nets.
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| CN111293308A (en) * | 2019-12-06 | 2020-06-16 | 河北科技大学 | Negative electrode material, negative electrode, potassium ion battery and preparation method |
| CN112687877A (en) * | 2020-12-24 | 2021-04-20 | 李树成 | Preparation method of super-high-magnification negative electrode material |
| 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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| CN116443853A (en) * | 2023-05-17 | 2023-07-18 | 赣州立探新能源科技有限公司 | Hard carbon and preparation method and application thereof |
| CN116477606A (en) * | 2023-06-21 | 2023-07-25 | 成都锂能科技有限公司 | Hard carbon material with uniformly distributed nitrogen and phosphorus as well as preparation method and application thereof |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101887966A (en) * | 2010-06-18 | 2010-11-17 | 深圳市贝特瑞新能源材料股份有限公司 | Composite hard carbon cathode material of lithium ion battery and preparation method thereof |
| CN101916845A (en) * | 2010-08-05 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon material for power and energy-storage battery and preparation method thereof |
| CN102683661A (en) * | 2012-06-01 | 2012-09-19 | 中国东方电气集团有限公司 | Method for preparing hard carbon negative electrode materials of lithium ion battery |
| KR20120131361A (en) * | 2011-05-25 | 2012-12-05 | 인하대학교 산학협력단 | Surface modification method of graphite-powder treated with phosphoric acid impregnation and manufacturing method of high efficient adsorbents for hydrogen storage |
| CN104600258A (en) * | 2014-12-26 | 2015-05-06 | 宁夏共享新能源材料有限公司 | Composite negative pole material for lithium ion batteries and preparation method thereof |
| CN105529443A (en) * | 2015-12-14 | 2016-04-27 | 湖南星城石墨科技股份有限公司 | Preparation method of hard carbon material for negative electrode of lithium-ion battery |
| CN105633380A (en) * | 2016-03-04 | 2016-06-01 | 中国科学院新疆理化技术研究所 | Preparation method for starch-based porous hard carbon negative electrode material of lithium ion battery |
| CN106133964A (en) * | 2014-03-31 | 2016-11-16 | 株式会社吴羽 | Non-aqueous electrolyte secondary cell negative electrode carbonaceous material, anode for nonaqueous electrolyte secondary battery electrode, rechargeable nonaqueous electrolytic battery and vehicle |
| CN106185862A (en) * | 2016-06-30 | 2016-12-07 | 中国科学院物理研究所 | A kind of pyrolyzed hard carbon material and application thereof |
| CN106299365A (en) * | 2016-11-04 | 2017-01-04 | 郑州大学 | A kind of sodium-ion battery biomass hard carbon cathode material, preparation method and sodium-ion battery |
-
2017
- 2017-12-13 CN CN201711326021.2A patent/CN109921018A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101887966A (en) * | 2010-06-18 | 2010-11-17 | 深圳市贝特瑞新能源材料股份有限公司 | Composite hard carbon cathode material of lithium ion battery and preparation method thereof |
| CN101916845A (en) * | 2010-08-05 | 2010-12-15 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon material for power and energy-storage battery and preparation method thereof |
| KR20120131361A (en) * | 2011-05-25 | 2012-12-05 | 인하대학교 산학협력단 | Surface modification method of graphite-powder treated with phosphoric acid impregnation and manufacturing method of high efficient adsorbents for hydrogen storage |
| CN102683661A (en) * | 2012-06-01 | 2012-09-19 | 中国东方电气集团有限公司 | Method for preparing hard carbon negative electrode materials of lithium ion battery |
| CN106133964A (en) * | 2014-03-31 | 2016-11-16 | 株式会社吴羽 | Non-aqueous electrolyte secondary cell negative electrode carbonaceous material, anode for nonaqueous electrolyte secondary battery electrode, rechargeable nonaqueous electrolytic battery and vehicle |
| CN104600258A (en) * | 2014-12-26 | 2015-05-06 | 宁夏共享新能源材料有限公司 | Composite negative pole material for lithium ion batteries and preparation method thereof |
| CN105529443A (en) * | 2015-12-14 | 2016-04-27 | 湖南星城石墨科技股份有限公司 | Preparation method of hard carbon material for negative electrode of lithium-ion battery |
| CN105633380A (en) * | 2016-03-04 | 2016-06-01 | 中国科学院新疆理化技术研究所 | Preparation method for starch-based porous hard carbon negative electrode material of lithium ion battery |
| CN106185862A (en) * | 2016-06-30 | 2016-12-07 | 中国科学院物理研究所 | A kind of pyrolyzed hard carbon material and application thereof |
| CN106299365A (en) * | 2016-11-04 | 2017-01-04 | 郑州大学 | A kind of sodium-ion battery biomass hard carbon cathode material, preparation method and sodium-ion battery |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN111293308B (en) * | 2019-12-06 | 2023-05-05 | 河北科技大学 | Negative electrode material, negative electrode, potassium ion battery and preparation method |
| CN113381016A (en) * | 2020-12-15 | 2021-09-10 | 中南林业科技大学 | Biomass hard carbon negative electrode material for sodium ion battery and preparation method and application thereof |
| CN113381016B (en) * | 2020-12-15 | 2022-08-02 | 中南林业科技大学 | Biomass hard carbon negative electrode material for sodium ion battery and preparation method and application thereof |
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| CN114956037A (en) * | 2022-05-13 | 2022-08-30 | 溧阳中科海钠科技有限责任公司 | Carbon material for sodium ion battery negative electrode, preparation method of carbon material, sodium ion battery negative electrode piece and sodium ion battery |
| 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 |
| CN115207350A (en) * | 2022-09-13 | 2022-10-18 | 中国科学院山西煤炭化学研究所 | Hard carbon negative electrode material of sodium ion battery with ultralow specific surface area and preparation method thereof |
| CN115806284A (en) * | 2022-10-21 | 2023-03-17 | 中科(宜兴)新材料研究有限公司 | Preparation method for improving yield of biomass-based hard carbon |
| CN115849332A (en) * | 2022-11-23 | 2023-03-28 | 广东工业大学 | High-rate hard carbon negative electrode material and preparation method and application thereof |
| CN116443853A (en) * | 2023-05-17 | 2023-07-18 | 赣州立探新能源科技有限公司 | Hard carbon and preparation method and application thereof |
| CN116477606A (en) * | 2023-06-21 | 2023-07-25 | 成都锂能科技有限公司 | Hard carbon material with uniformly distributed nitrogen and phosphorus as well as preparation method and application thereof |
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