CN109921020A - A kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material - Google Patents
A kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material Download PDFInfo
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Abstract
The present invention relates to technical field of lithium ion, specifically a kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material includes the following steps: to prepare carbon source presoma powder；Carbon source presoma powder is mixed with oxidant；Mixture successively carries out low-temperature oxidation reaction, high-temperature oxydation reaction；Pre- carbonization treatment, carbonization treatment.Compared with the existing technology, the basis material that can be synthesized extensively using organic carbon sources such as resin, pitches as hard charcoal, raw material sources are extensive by the present invention, help somewhat to reduce production cost；And preparation process is simple, mild condition is controllable, helps to improve product batches stability, is suitble to industrialization continuous production；The high capacity hard charcoal negative electrode material of preparation has high discharge capacity and first charge-discharge efficiency, the high comprehensive performance of manufactured button cell.
Description
Technical field
The present invention relates to technical field of lithium ion, specifically a kind of high-capacity lithium ion cell hard charcoal cathode material
The preparation method of material.
Background technique
In energy storage field, traditional secondary cell such as lead-acid battery, ickel-cadmium cell, nickel-metal hydride battery, because of energy density
It is small, open-circuit voltage is low, service life is short, pollute environment, have the shortcomings that memory effect and self-discharge rate is big without being able to satisfy just
Take the needs of formula electronic product development.The energy density of lithium ion secondary battery Yin Qigao, stable charge and discharge platform, wide work
Make temperature range, low self-discharge rate, length cycle life and it is environmentally friendly the advantages that, become in new energy field
Primary study object.Other than meeting the diversified growth requirement of electronic product, lithium ion secondary battery is also electric car
(EV), the ideal source of hybrid vehicle (HEV).Make electric car that there is satisfactory course continuation mileage and keeps needing
Speed, energy storage device material therefor must have high-energy density, high power density and safety.
Hard charcoal negative electrode material due to huddling three-dimensional carbon structure with special, be more suitable for using under high current charge-discharge and
It is concerned.Good safety and splendid cyclical stability make it be expected to quickly be applied on electric car.
Patent CN1947286A proposes to prepare porosity pitch using cross-linking reaction method, then through the obtained difficult stone of air oxidation
The hard carbon material of inkization.There are the tediously long complexity of preparation process, high production cost for this method, thus are difficult to realize be commercialized.In
State patent CN103754858A proposes to prepare hard charcoal material through repeatedly solidification and carbonization treatment using high molecular polymer and crosslinking agent
Material, it is cumbersome to equally exist preparation process, is not suitable for the problems such as high-volume is commercially produced.
Summary of the invention
The purpose of the present invention is overcome in the prior art complex process, it is at high cost, be difficult to industrialized defect, one kind is provided
Simple process, raw material sources are extensive and at low cost, excellent electrochemical performance, the hard charcoal negative electrode material of performance stable and consistent.
To achieve the above object, a kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material, feature are designed
It is, including following preparation step:
(1), carbon source presoma is crushed to and is crossed 80 mesh screens, extracting screen underflow obtains the carbon source forerunner that D50 partial size is 8~10 μm
Body powder；The carbon source presoma is at least one of high softening point bitumen, copna resin, phenolic resin or epoxy resin；
(2), carbon source presoma powder is mixed with oxidant in mass ratio 100: 1~100: 50, obtains uniform mix
Close material；The oxidant be concentration be 10~30% hydrogen peroxide, concentration is 80~98% concentrated sulfuric acids, concentration is 10~68% nitre
At least one of acid, the pure potassium permanganate of analysis, the pure ammonium persulfate of analysis, the pure sodium peroxydisulfate of analysis or the pure potassium peroxydisulfate of analysis；
When mixing when oxidant uses liquid with carbon source presoma powder progress liquid phase, also need that dispersing agent, the carbon source forerunner is added
The mass ratio of body powder and dispersing agent is not more than 60: 100；The dispersing agent is deionized water；
(3), gained mixture is first with oxidation reaction 1~10 hour under 50~100 DEG C of low temperature, then with 110~250 DEG C of high temperature
Lower oxidation reaction 1~10 hour is cooled to the carbon source presoma that room temperature must be oxidized；
(4), the carbon source presoma that gained is oxidized under inert gas protection, carries out pre- carbonization treatment with 500~700 DEG C
0.5~6 hour, it is cooled to room temperature；
(5), gained powder under inert gas protection, with 800~1300 DEG C progress carbonization treatment 1~6 hour, be cooled to
Room temperature is sieved up to high-capacity lithium ion cell hard charcoal negative electrode material.
High softening point bitumen is the coal tar pitch or high temperature asphalt that softening point is 200~300 DEG C.
The copna resin is the thermoplastic obtained by thermal plastic polymer reacts under acid medium with crosslinking agent
Type polymer: crosslinking agent: the mass parts ratio of acid medium is 100: 100: 1~100: 10: 20, and reaction temperature is 120~250
DEG C, the reaction time is 2~6 hours；
The thermal plastic polymer be Petropols, pitch, acrylic resin, furane resins, polyethylene, polyvinyl chloride,
At least one of polystyrene or polyamide；
The acid medium is at least one of methanesulfonic acid, p-methyl benzenesulfonic acid, naphthalene sulfonic acids or concentrated sulfuric acid；
The crosslinking agent is metaformaldehyde, terephthalaldehyde, benzaldehyde, benzyl alcohol, terephthalyl alcohol, furfural and formaldehyde
At least one of.
When the carbon source presoma powder and solid oxidizer carry out solid phase mixing, carries out, mix in high speed mixer
Material rate is 200~800r/min, and mixing time is 5~60min；
When the carbon source presoma powder, which carries out liquid phase with liquid oxidizer, to be mixed, carries out, stir in high-speed mixer
Mixing rate is 500~5000r/min, and mixing time is 5~60min.
The oxidation reaction using a kind in air dry oven, vacuum oven, Muffle furnace, batch-type furnace or shaft furnace or
At least two kinds of combinations, also can be first dry in a kind of equipment, enters back into another equipment and continues drying.
The heating rate of the pre- carbonization treatment is 0.5~20 DEG C/min；The heating rate of the carbonization treatment be 0.5~
20℃/min。
The pre- carbonization treatment carries out in shaft furnace.
The carbonization treatment carries out in atmosphere furnace.
Inert atmosphere in the pre- carbonization treatment and carbonization treatment is respectively adopted in nitrogen, helium or argon gas at least
It is a kind of.
The crushing is one or more of ball milling, mechanical crushing, air-flow crushing mode.Gas is preferably used in the present invention
Stream crushes, and 8~9Mpa of compressed air pressure, the loading frequency of air-flow crushing are 15~25Hz.
The present invention compared with the existing technology, the base that can be synthesized extensively using organic carbon sources such as resin, pitches as hard charcoal
Body material, raw material sources are extensive, help somewhat to reduce production cost；And preparation process is simple, mild condition can
Control, helps to improve product batches stability, is suitble to industrialization continuous production；The high capacity hard charcoal negative electrode material of preparation has height
Discharge capacity and first charge-discharge efficiency, the high comprehensive performance of manufactured button cell mainly have the advantage that (1) electricity
Chemical property is good, and reversible capacity is high, and first charge-discharge efficiency is 79% or more；(2) to electrolyte and other additive adaptability
Preferably, cyclicity is excellent；(3) safety is preferable；(4) product property is stablized, almost without difference between batch.The present invention is mentioned
The high capacity spherical shape hard charcoal negative electrode material of confession has higher in fields such as electric tool, hybrid vehicle, electronic product, energy storage
Application value, can satisfy requirement of the high performance lithium ion battery to negative electrode material charge-discharge performance.
Specific embodiment
The present invention is further described now in conjunction with embodiment.But therefore do not limit the present invention to the implementation
Among example range.
Embodiment 1
1, by softening point be 280 DEG C high temperature asphalt using the crushing of jet mill grinding machine, volume is made and is averaged grain
The powder that diameter D50 is 9 μm；It is crushed in this example preferably using air-flow crushing mode, the compressed air pressure 8 of air-flow crushing~
9Mpa, loading frequency are 15~25Hz；
2, the resulting pitch powder of 1000g is fed intake in stir mixing machine and in 500r/ together with 100g ammonium persulfate
Discharging obtains mixture after mixing 5min under min revolving speed；
3, gained mixture is placed in after 80 DEG C of air dry oven reaction 2h and is warming up to 150 DEG C again the reaction was continued 2h, it is cold
But to the asphalt powder that discharging after room temperature is oxidized；
4, 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
Temperature discharging；
5, it is reloaded into atmosphere furnace 2 DEG C/min under nitrogen protection and is warming up to 1200 DEG C of carbonization 1h, be cooled to room temperature discharging
Up to hard charcoal negative electrode material.
The environment temperature that signified room temperature is 0~80 DEG C in the present invention.
Embodiment 2
1, by softening point be 280 DEG C high temperature asphalt using the crushing of jet mill grinding machine, volume is made and is averaged grain
The powder that diameter D50 is 9 μm；
2, the resulting pitch powder of 1000g is fed intake in stir mixing machine and in 500r/ together with 200g ammonium persulfate
Discharging obtains mixture after mixing 5min under min revolving speed；
3, gained mixture is placed in after 100 DEG C of air dry oven reaction 2h and is warming up to 200 DEG C again the reaction was continued 2h, it is cold
But to the asphalt powder that discharging after room temperature is oxidized；
4, 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
Temperature discharging；
5, it is reloaded into atmosphere furnace 2 DEG C/min under nitrogen protection and is warming up to 1200 DEG C of carbonization 1h, be cooled to room temperature discharging
Up to hard charcoal negative electrode material.
Embodiment 3
1, by softening point be 280 DEG C high temperature asphalt using the crushing of jet mill grinding machine, volume is made and is averaged grain
The powder that diameter D50 is 9 μm；
2, feed intake together with the hydrogenperoxide steam generator for being 20% by the resulting pitch powder of 1000g and 1000g mass concentration in
Discharging obtains slurry in blender and under 500r/min revolving speed after mixing 20min；
3, gained slurry is placed in after 80 DEG C of air dry oven reaction 2h and is warming up to 110 DEG C again the reaction was continued 4h, it is cooling
Discharge the asphalt powder being oxidized after to room temperature；
4, 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
Temperature discharging；
5, it is reloaded into atmosphere furnace 2 DEG C/min under nitrogen protection and is warming up to 1200 DEG C of carbonization 1h, be cooled to room temperature discharging
Up to hard charcoal negative electrode material.
Embodiment 4
1, the coal tar pitch that softening point is 250 DEG C is crushed using jet mill grinding machine, volume average particle size is made
The powder that D50 is 9 μm；
2, the resulting pitch powder of 1000g is fed intake together with the nitric acid solution that 1000g mass concentration is 20% in stirring
Discharging obtains slurry in machine and under 500r/min revolving speed after mixing 20min；
3, gained slurry is placed in after 80 DEG C of air dry oven reaction 2h and is warming up to 110 DEG C again the reaction was continued 4h, it is cooling
Discharge the asphalt powder being oxidized after to room temperature；
4, 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
Temperature discharging；
5, it is reloaded into atmosphere furnace 2 DEG C/min under nitrogen protection and is warming up to 1200 DEG C of carbonization 1h, be cooled to room temperature discharging
Up to hard charcoal negative electrode material.
Embodiment 5
1, thermoset phenolic resin is crushed using jet mill grinding machine, the powder that volume average particle size D50 is 9 μm is made
Body；
2, the resulting the tree powder body of 1000g is fed intake in stir mixing machine and in 500r/ together with 200g ammonium persulfate
Discharging obtains mixture after mixing 5min under min revolving speed；
3, gained mixture is placed in after 80 DEG C of air dry oven reaction 2h and is warming up to 200 DEG C again the reaction was continued 1h, it is cold
But to the resin-oatmeal that discharging after room temperature is oxidized；
4, 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
Temperature discharging；
5, it is reloaded into atmosphere furnace 2 DEG C/min under nitrogen protection and is warming up to 1200 DEG C of carbonization 1h, be cooled to room temperature discharging
Up to hard charcoal negative electrode material.
Embodiment 6
1, copna resin is crushed using jet mill grinding machine, the powder that volume average particle size D50 is 9 μm is made；
2, by the resulting copna resin powder of 1000g feed intake in stir mixing machine together with 150g ammonium persulfate and in
Discharging obtains mixture after mixing 5min under 500r/min revolving speed；
3, gained mixture is placed in after 80 DEG C of air dry oven reaction 2h and is warming up to 150 DEG C again the reaction was continued 2h, it is cold
But to the resin-oatmeal that discharging after room temperature is oxidized；
4, 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
Temperature discharging；
5, it is reloaded into atmosphere furnace 2 DEG C/min under nitrogen protection and is warming up to 1200 DEG C of carbonization 1h, be cooled to room temperature discharging
Up to hard charcoal negative electrode material.
Wherein, the copna resin is by 120 DEG C of coumarone indene resins of softening point, metaformaldehyde and p-methyl benzenesulfonic acid by matter
Amount is warming up to 180 DEG C of progress cross-linked polymerics than 20: 12: 1 mixed material feedings in reaction kettle and under nitrogen atmosphere and stirring condition
4h is reacted, then is cooled to room temperature after being warming up to 450 DEG C of reaction 4h and obtains.
Comparative example 1
1, by softening point be 280 DEG C high temperature asphalt using the crushing of jet mill grinding machine, volume is made and is averaged grain
The powder that diameter D50 is 9 μm；
2, it is warming up to 150 DEG C of continuation again after the resulting pitch powder of 1000g to be placed in 80 DEG C of air dry oven processing 2h
2h is handled, is discharged after being cooled to room temperature；
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
Temperature discharging；
4, it is reloaded into atmosphere furnace 2 DEG C/min under nitrogen protection and is warming up to 1200 DEG C of carbonization 1h, be cooled to room temperature discharging
Up to the comparison hard charcoal negative electrode material.
Comparative example 2
1, copna resin is crushed using jet mill grinding machine, the powder that volume average particle size D50 is 9 μm is made；
2, it is warming up to 150 DEG C of continuation again after the resulting the tree powder body of 1000g to be placed in 80 DEG C of air dry oven processing 2h
2h is handled, is discharged after being cooled to room temperature；
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
Temperature discharging；
4, it is reloaded into atmosphere furnace 2 DEG C/min under nitrogen protection and is warming up to 1200 DEG C of carbonization 1h, be cooled to room temperature discharging
Up to hard charcoal negative electrode material.
Wherein, the copna resin be by 120 DEG C of softening point of coumarone indene resin, metaformaldehyde and p-methyl benzenesulfonic acid by
20: 12: 1 mixed material feeding of mass ratio, which is warming up to 180 DEG C in reaction kettle and under nitrogen atmosphere and stirring condition and be crosslinked, to be gathered
Reaction 4h is closed, then is cooled to room temperature after being warming up to 450 DEG C of reaction 4h and obtains.
Partial size, real density, vibration are carried out respectively to the hard charcoal negative electrode material in Examples 1 to 6 and comparative example 1~2
As a result the test of real density and specific surface area is listed in table 1.Instrument title used in testing and model are as follows: partial size: Malvern
Laser particle size analyzer MS2000；Real density: the full-automatic real density analyzer of U.S.'s health tower UltraPYC 1200e type；Vibration density
Degree: tap density tester FZS4-4B；Specific surface area: health tower specific surface area measuring instrument NOVA2000e.
The hard charcoal negative electrode material in Examples 1 to 6 and comparative example 1~2 is carried out for the first time using half-cell test method
Electric performance test and cycle performance test are detained, table 1 is as a result listed in.The test method of half-cell are as follows: be with N-Methyl pyrrolidone
Solvent prepares the Kynoar solution that mass fraction is 6~7%, and hard charcoal negative electrode material, Kynoar, conductive carbon black are pressed
Mass ratio 90: 5: 5 is uniformly mixed, and is applied on copper foil, and it is that vacuum is done in 110 DEG C of vacuum ovens that the pole piece coated, which is put into temperature,
Dry 4 hours spare.Then 2430 type button cells are assembled into that glove box of the German meter Kai Luo of applying argon gas, with 1mol/L
The three component mixed solvents of LiPF6 are electrolyte by EC: DMC: EMC=1: 1: 1 (volume ratio) mixed liquor, and metal lithium sheet is to electricity
Pole carries out electrochemical property test, charging/discharging voltage range to the half-cell of assembling on U.S.'s Arbin electrochemical detection system
For 0mV to 2.0V, reversible capacity, for the first time coulombic efficiency and cycle performance for the first time are tested under 0.1C.Coulombic efficiency=for the first time for the first time
The discharge capacity of charging capacity/for the first time.Obtained half-cell performance parameter is as shown in table 1.
Table 1
Hard charcoal negative electrode material electrical performance data in 1~6 in conjunction with the embodiments, it is known that the carbon source kind of selection, oxidant kind
Class and oxidation technology produce bigger effect the performance of final hard charcoal negative electrode material.Using high softening-point asphalt as raw material,
Reversible capacity reaches 401mAh/g to 1 gained hard charcoal cathode of embodiment for the first time at 0.1C, and coulombic efficiency is 83.1% for the first time.And for
Embodiment 2 can get the appearance reversible for the first time of up to 420mAh/g when increasing oxidant additional proportion and changing oxidation technology
Amount, coulombic efficiency is 81.1% for the first time.When changing oxidant species, 3 gained hard charcoal cathode of embodiment reversible capacity for the first time
For 398mAh/g, coulombic efficiency is 83.3% for the first time.Using high softening-point coal tar pitch as raw material, 4 gained hard charcoal cathode of embodiment
Reversible capacity is 373mAh/g for the first time under 0.1C, and coulombic efficiency is 80.8% for the first time.Using phenolic resin as raw material, 5 institute of embodiment
Obtaining hard charcoal cathode, reversible capacity is up to 352mAh/g for the first time, and coulombic efficiency is 79.3% for the first time.It is real using copna resin as raw material
Applying 6 gained hard charcoal cathode of example, reversible capacity is up to 412mAh/g for the first time, and coulombic efficiency is 80.4% for the first time.It is hard obtained by each embodiment
Charcoal cathode has good cyclical stability, and 100 times circulation volume conservation rate is higher than 98.5%.
In comparison, the reversible capacity for the first time of 2 gained hard charcoal cathode of comparative example 1 and comparative example is far below implementation
1~6 gained hard charcoal cathode of example shows that oxidation technology according to the present invention can effectively improve the characteristic of gained hard charcoal product,
Be conducive to improve the reversible capacity of battery, coulombic efficiency and keep excellent cycle performance.Compared with the traditional graphite negative electrode, this hair
Bright lithium ion battery hard charcoal negative electrode material has higher capacity and excellent cyclical stability, has in power battery field
Broad application prospect.
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.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (10)
1. a kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material, which is characterized in that including following preparation step:
(1), carbon source presoma is crushed to and is crossed 80 mesh screens, extracting screen underflow obtains the carbon source precursor that D50 partial size is 8~10 μm
Body；The carbon source presoma is at least one of high softening point bitumen, copna resin, phenolic resin or epoxy resin；
(2), carbon source presoma powder is mixed with oxidant in mass ratio 100: 1~100: 50, obtains uniform mixture；
The oxidant be concentration be 10~30% hydrogen peroxide, concentration is 80~98% concentrated sulfuric acids, concentration be 10~68% nitric acid, analysis
At least one of pure potassium permanganate, the pure ammonium persulfate of analysis, the pure sodium peroxydisulfate of analysis or the pure potassium peroxydisulfate of analysis；Work as oxidant
Using when liquid with carbon source presoma powder carry out liquid phase mix when, also need be added dispersing agent, the carbon source presoma powder with
The mass ratio of dispersing agent is not more than 60: 100；The dispersing agent is deionized water；
(3), gained mixture is first with oxidation reaction 1~10 hour under 50~100 DEG C of low temperature, then with oxygen under 110~250 DEG C of high temperature
Change reaction 1~10 hour, is cooled to the carbon source presoma that room temperature must be oxidized；
(4), the carbon source presoma that gained is oxidized under inert gas protection, carries out pre- carbonization treatment 0.5 with 500~700 DEG C
~6 hours, it is cooled to room temperature；
(5), gained powder under inert gas protection, with 800~1300 DEG C progress carbonization treatment 1~6 hour, be cooled to room
Temperature is sieved up to high-capacity lithium ion cell hard charcoal negative electrode material.
2. a kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material as described in claim 1, which is characterized in that
High softening point bitumen is the coal tar pitch or high temperature asphalt that softening point is 200~300 DEG C.
3. a kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material as described in claim 1, which is characterized in that
The copna resin is obtained by thermal plastic polymer reacts under acid medium with crosslinking agent, and the thermoplastics type is poly-
Close object: crosslinking agent: the mass parts ratio of acid medium is 100: 100: 1~100: 10: 20, and reaction temperature is 120~250 DEG C,
Reaction time is 2~6 hours；
The thermal plastic polymer is Petropols, pitch, acrylic resin, furane resins, polyethylene, polyvinyl chloride, polyphenyl
At least one of ethylene or polyamide；
The acid medium is at least one of methanesulfonic acid, p-methyl benzenesulfonic acid, naphthalene sulfonic acids or concentrated sulfuric acid；
The crosslinking agent is in metaformaldehyde, terephthalaldehyde, benzaldehyde, benzyl alcohol, terephthalyl alcohol, furfural and formaldehyde
It is at least one.
4. a kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material as described in claim 1, which is characterized in that
It when the carbon source presoma powder and solid oxidizer carry out solid phase mixing, is carried out in high speed mixer, mixing speed
Rate is 200~800r/min, and mixing time is 5~60min；
It when the carbon source presoma powder, which carries out liquid phase with liquid oxidizer, to be mixed, is carried out in high-speed mixer, stirring speed
Rate is 500~5000r/min, and mixing time is 5~60min.
5. a kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material as described in claim 1, which is characterized in that
The oxidation reaction is using a kind or at least two kinds of in air dry oven, vacuum oven, Muffle furnace, batch-type furnace or shaft furnace
Combination.
6. a kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material as described in claim 1, which is characterized in that
The heating rate of the pre- carbonization treatment is 0.5~20 DEG C/min；The heating rate of the carbonization treatment be 0.5~20 DEG C/
min。
7. a kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material as described in claim 1, which is characterized in that
The pre- carbonization treatment carries out in shaft furnace.
8. a kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material as described in claim 1, which is characterized in that
The carbonization treatment carries out in atmosphere furnace.
9. a kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material as described in claim 1, which is characterized in that
At least one of nitrogen, helium or argon gas is respectively adopted in inert atmosphere in the pre- carbonization treatment and carbonization treatment.
10. a kind of preparation method of high-capacity lithium ion cell hard charcoal negative electrode material as described in claim 1, feature exist
In the crushing is one or more of ball milling, mechanical crushing, air-flow crushing mode.
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| CN112645300A (en) * | 2019-11-07 | 2021-04-13 | 上海杉杉科技有限公司 | Hard carbon negative electrode material, lithium ion battery and preparation method and application thereof |
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| CN117326546A (en) * | 2023-11-24 | 2024-01-02 | 成都锂能科技有限公司 | Lignin-phenolic resin-based hard carbon material and preparation method and application thereof |
| CN117326546B (en) * | 2023-11-24 | 2024-02-06 | 成都锂能科技有限公司 | Lignin-phenolic resin-based hard carbon material and preparation method and application thereof |
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