CN104766955A - Method for recycling natural graphite fine powder as negative pole material - Google Patents
Method for recycling natural graphite fine powder as negative pole material Download PDFInfo
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- CN104766955A CN104766955A CN201510200512.7A CN201510200512A CN104766955A CN 104766955 A CN104766955 A CN 104766955A CN 201510200512 A CN201510200512 A CN 201510200512A CN 104766955 A CN104766955 A CN 104766955A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a method for recycling natural graphite fine powder as a negative pole material. The method comprises the following steps: step A) taking 'tail material' produced in the production process of the natural graphite negative pole material of a lithium battery as raw material, adding a bonding agent and a pore-forming agent, performing kneading and granulation at a certain temperature, further performing roller pressing or pressing and performing carbonization at high temperature; step B) crushing, shaping and nodulizing the material after carbonization to obtain spherical or oval graphite powder which is in line with the requirement on particle size range, further performing high-temperature graphitizing and meanwhile, adding the 'tail material' which is re-collected in the crushing/nodulizing process into the step A) for recycling as the raw material; and step C) performing particle size allocation on the powder after nodulizing treatment and filling the powder into gaps between particles. The preparation method provided by the invention is safe and controllable in process; and by adopting the preparation method, the recycling of the low-value graphite 'tail material' is realized, and the prepared negative pole material has the advantages of good performances, and good recycling, rate charge and discharge and low-temperature performances.
Description
Technical field
The invention belongs to energy field, relate to a kind of method of negative material, particularly relate to a kind of with the superfine graphite powder produced in natural graphite negative electrode material production process-" tailing " for raw material, by process carry out cycling and reutilization, as the method for lithium ion battery negative material.
Background technology
Along with the development of automobile industry, the exhaustion of the non-renewable fossil fuel such as oil, natural gas receives publicity day by day, and air pollution and room temperature effect also become global problem.For solving energy problem, realize low-carbon environment-friendly, based on the development level of current energy technology, electric vehicle engineering becomes the emphasis direction of global economic development gradually, the countries such as the U.S., Japan, Germany, China in succession limit fuel vehicle and use, and greatly develop electric motor car.As the core component of electric automobile---electrokinetic cell has also welcome large good opportunity to develop.Electrokinetic cell refers to the battery being applied to electric motor car, comprise lithium ion battery, lead-acid battery, fuel cell etc., wherein, specific energy is high, specific power is large, self discharge is few because having for lithium ion battery, long service life and the advantage such as fail safe is good, has become the emphasis of current various countries development.And as the graphite type material of lithium ion battery negative material, there is lower lithium embedding/deintercalation current potential, suitable reversible capacity and aboundresources, the advantage such as cheap, be more satisfactory lithium ion battery negative material.
Graphite, as a kind of strategic resource, is not only widely used in general industry and consumer field, is also widely used in the industrial circle that some are special.But the at present low-end unordered exploitation that causes of the market demand of expanding day, causes adverse effect to the protection of resources of China and industrial upgrading.Graphite as negative material in process of production, all needs after graphite raw material is repeatedly pulverized by pulverizer, then carries out repeatedly nodularization by balling machine to it.Adopt this kind of technique, there is the shortcomings such as utilization rate of raw materials is low, environment is poor, because pulverizing and nodularization all need by receiving intermediate semi-finished products carries out process next time again after classification at every turn, and each classification all will reduce raw-material utilance, so the final rate of finished products half of the mode of production of this kind of negative material is 40% ~ 50%.Remaining 50% ~ 60% has just become " tailing ", graphite fine powder-" tailing " its particle diameter is little, specific area is high, tap density is low, lithium ion battery negative material can not be used as again, therefore value is extremely low, be mainly used in the aspects such as Ferrous Metallurgy to use as carburant, which not only adds production cost, also create the waste of resource.
Simultaneously, for various traditional modification mode of graphite, mainly based on material with carbon-coated surface, by one deck RESEARCH OF PYROCARBON coated on graphite top layer, effectively can stop the effect of organic solvent and graphite body, thus prevent the caused graphite linings of inserting altogether of lithium ion and electrolyte to peel off and efflorescence.And all only adopt the hard charcoal precursor of resinae or pitch class soft charcoal precursor separately as the clad material on top layer.
Adopt resinae as clad material, major advantage is resin good fluidity at low temperatures, can not only clad surface, and penetrate into graphite granule inside easily via the micropore in graphite, useful to the tap density and electronic conductivity that improve graphite granule, can also by heating, introduce the solidification of the method such as catalyst or Ultraviolet radiation, distortion can not be melted in resin pyrolytic process, also obvious expansion can not be produced, the degree of order of the amorphous carbon formed after resin pyrolysis is low, structure comparison is loose, lithium ion can embed relatively freely wherein and deviate from and can not produce large impact to its structure, therefore efflorescence is less likely to occur.But, the affinity of resinous material and graphite is poor, therefore the Carbon Materials that obtains of their pyrolysis and graphite are in conjunction with insecure, the Carbon Materials yield obtained by resin pyrolysis is on the low side, enbrittle, in resin pyrolytic process, fugitive constituent is many, specific area is higher, the cohesive force of resin is stronger, be easy to cause coated particle to bond together, the destruction of coating layer is easily caused when pulverizing after heat treatment, resin is in heat treatment process simultaneously, Small molecular in resin is too much, the surface of coated rear material can be caused in overflow process to produce too much space, cause coated after the specific area of graphite excessive and cause irreversible capacity first excessive.
These problems above, have impact on the compressibility of the cycle efficieny of resin-coating graphite material, cyclical stability and graphite electrode.And adopt pitch, petroleum tar, coal tar or their mixture coated graphite, asphalt pyrolysis charcoal is less than the specific area of From Resin Char coated graphite, to get well with the affinity of graphite, structure is more firm, but pitch-coating is out of shape because of fusing in heating process, consumption too much also easily causes the mutually bonding of Coating Graphite Particles, consumption is very few easily cause coated uneven, and be easy in heating process expand, affect the electrical property of graphite.
Summary of the invention
In order to solve above technical problem, the invention provides native graphite fine powder and recycling method as negative material, comprising following step:
Steps A: be raw material by " tailing " that produce in lithium battery natural graphite negative electrode material production process, add binding agent, pore creating material, at higher than asphalt softening point temperature 20 ~ 50 DEG C, carry out kneading granulation, then carry out roll-in or compacting, at high temperature 800 ~ 1000 DEG C, carry out carbonization;
Step B: the material after carbonization was entered pulverizing, shaping nodularization, obtains the spherical or oval graphite composite powder meeting particle size range requirement; More than 2600 DEG C, carry out high temperature graphitization, can " tailing " collected in pulverizing/nodularization process be added to steps A simultaneously and use as feedstock circulation;
Step C: carry out granularity allocation to the powder after graphitization processing, adds a certain proportion of natural modified graphite cathode powder, is filled into the gap between particle, improves its bulk density by the mode of physical mixed.
Wherein, graphite composite powder, by tap density measuring instrument, constantly vibrates, can record the packing density of powder.But due to powder shape subglobular or ellipse, the contact between powder granule is point cantact or small size contact, wherein appoints and so leaves space, simultaneously the limitation of pulverizing and nodularization equipment, and the tap density of powder is still difficult to promote.By adding a certain amount of fine powder in powder after shaping spheroidising, being filled in space, can further improve the bulk density of material monolithic.
Lithium ion battery is a kind of rechargeable battery, it mainly rely on lithium ion between a positive electrode and a negative electrode movement carry out work.In charge and discharge process, Li+ comes and goes between two electrodes and embeds and deintercalation: during rechargable battery, and Li+ is from positive pole deintercalation, and embed negative pole through electrolyte, negative pole is in rich lithium state; Then contrary during electric discharge.And graphite cathode material is owing to having good layer structure, be applicable to the embedding-deviate from and form Intercalation reaction formula compound L iC of lithium
x, and there is good charge and discharge platform, be therefore subject to extensive use.And graphite is as lithium ion battery negative material, rushing in electric process first, graphite and electrolyte interface can generate SEI film by interfacial reaction, cause the loss of irreversible capacity, therefore, the theoretical capacity of graphite cathode material is 372mAh/g, but in actual use, its capacity plays and is generally 330 ~ 360 mAh/g, lower than theoretical capacity.And the specific area that SEI film produces irreversible capacity loss and the graphite cathode material caused has direct relation, the specific area of graphite is large, and the scope of electrolyte and graphite contact is large, and the SEI of generation is too much, and the irreversible capacity loss caused is also larger.Meanwhile, because graphite is especially in the electrolyte containing PC, easy and electrolyte occurs embedding altogether, and causes graphite flake layer to peel off, and forms new end face, causes further SEI to be formed, cause cycle performance constantly to reduce.Therefore, the graphite coat modification generally adopted at present, excessive for the specific area of graphite exactly and carry out coated one deck modified layer to reduce the specific area of material, thus improve the discharging efficiency first of graphite, promote its capacity and play and stable circulation performance.
And the tailing produced in natural graphite negative electrode material production process, its particle thin (D50 is generally 1 ~ 7 μm), specific area high (SSA >=10 ㎡/g), tap density low (Tap≤0.6g/cm3), although itself structure is graphite laminate structure, there is certain capacity, but it is as negative material, there is the shortcomings such as volumetric specific energy is low, capacity performance is low, materials processing poor performance, use as carburant because the processing mode for tailing in the industry is mainly used in the aspects such as Ferrous Metallurgy.But along with continuous popularization and the fast development of electric automobile, the market demand of graphite cathode material also presents the situation increased fast, while negative material output constantly expands, the quantity size of tailing also increases thereupon, therefore, high added value process is carried out and recycles to have wide market prospects to tailing.
The present invention adopts above technical scheme, and its advantage is, and 1, the tailing that produces in industrial production natural graphite negative electrode material, particle diameter is little, and specific area is large, and processing mode general in industry processes as the carburant that added value is very low.But just because its particle diameter is little, so the channel resistance that lithium ion enters graphite layers can be shortened, showing more excellent high rate performance and cryogenic property.2, interpolation pitch and resin are as adhesive, carry out kneading granulation at a certain temperature, graphite small-particle is polymerized, again by roll-in or compacting, make internal structure careful further, improve its bulk density, then at high temperature carbonization is carried out, pitch and resin form RESEARCH OF PYROCARBON, and the Small molecular simultaneously in resin forms hole at material internal in being heated and overflowing, and these micropores are conducive to the contact range expanding graphite and lithium ion deintercalation.3, graphitization makes material internal change three-dimensional orderly overlapping into from the unordered overlapping of two-dimensional space, allows material structure structure be tending towards complete, improves cyclical stability and the homogeneity of product of material further.4. control the particle diameter Dmax of product, in negative electrode material powder, size indicator Dmax is a very crucial technical parameter, and be especially applied in automobile power cell, the security performance of this index to electrokinetic cell plays very crucial effect.If there is the graphite granule that particle diameter is bigger than normal in material powder, in electrokinetic cell quick charge process, the passage entering graphite layers due to lithium ion increases, and it is excessive to embed electric current, and surface can be caused to analyse lithium, forms dendrite, pierces through barrier film, causes potential safety hazard.5, the later stage is again by granularity allocation, avoids material and causes tap density to be difficult to the difficult problem promoted further by simple mechanical process, improve its volume energy density.
Preferably, heating rate 1 ~ 10 DEG C/min in steps A.
Preferably, the particle diameter D50 of described raw material is 1 ~ 7 μm; Tap density≤0.6g/cm
3, specific area>=10 ㎡/g.
Preferably, in steps A, binding agent adopts modified coal tar pitch, and described modified coal tar pitch adopts one or more in coal tar pitch, petroleum asphalt, mesophase pitch, modified coal tar pitch.
Preferably, in steps A pore creating material be phenolic resins, epoxy resin, polyvinyl alcohol, Corvic, polyamide one or more.
Preferably, graphite in described steps A: binding agent: the weight ratio of pore creating material is 100:0.1 ~ 0.4:0.01 ~ 0.1.
Preferably, granularity allocation in described step C, the weight ratio of the graphite after carbonization and the graphite composite powder of interpolation is 1:0.05 ~ 0.2, and wherein, the natural modified graphite composite powder particle diameter of interpolation is less than the powder obtained in step B.
In described step B, the average grain diameter D50 obtained after pulverizing, shaping nodularization is 8 ~ 25 μm, Dmax≤55.
Electrokinetic cell is as the core component of new-energy automobile, compared with the conventional lithium-ion battery used in daily life, to material, there is more harsh standard and requirement, as high-rate charge-discharge capability, good high temperature performance, overlength cycle performance, high safety performance and lower cost etc.And tailing has less particle diameter just because of it, the path of lithium ion turnover graphite layers is reduced, and therefore itself has very excellent multiplying power charge and discharge performance.
Use tailing is raw material, saves the cost of raw material, by carrying out " granulation " tailing, adding pitch as adhesive, making tailing particulate polymeric, change the shortcomings such as its bulk density is low, specific area is high, then carry out roll-in or compacting, improving its density further.Resin is as pore creating material, and in heat treatment process, the Small molecular in resin is too much, in overflow process, form micropore at material internal, then through pulverizing and can obtaining can be used for negative material appropriate particle size, isotropic powder after Shape correction.Micropore is convenient to absorption and the maintenance of electrolyte, and isotropism has anti-PC electrolyte advantage embedding altogether, ensures the performance of high temperature performance.After high temperature graphitization, make pitch and the resin of interpolation, change from disordered carbon Rotating fields to ordered structure, improve the purity of material monolithic simultaneously, reduce its magazine content, the consistency to ensure batch, increases the cyclical stability of material and security performance.
Preparation method's process safety of the present invention, controlled, achieve the cyclic utilization of waste, and obtained negative material is functional, shows good electrical property.
Embodiment
Below in conjunction with embodiment, preferably embodiment of the present invention is described in further detail:
Embodiment 1
With 100Kg native graphite " tailing " (particle diameter D50=3.46 μm, tap density 0.47g/cm
3, specific area 15.6m
2/ g) be raw material, in graphite: pitch: the ratio of pore creating material=100:0.2:0.05, take the modified coal asphalt (softening point 120 DEG C) of 20Kg, the epoxy resin (softening point 80 DEG C) of 5Kg, put in the kneader with heater together, while mixing, kneader is warming up to 140 DEG C (higher than asphalt softening point 20 DEG C).Be mixed together 120min, then suppress with the material notice tablet press machine that kneading is good, improve its bulk density.By the material after compacting under inert gas shielding, rise to 900 DEG C with the heating rate of 10 DEG C/min, and be incubated one hour, be then cooled to room temperature.
Material after high temperature cabonization is by coarse crushing, shaping nodularization, and control the particle diameter Dmax of material, obtaining particle diameter D50 is 16.52 μm, and tap density is 0.89 g/cm
3, the powder of specific area 5.1 ㎡/g, then by high temperature graphitization (2600 DEG C) process, improve material property further, material internal structure is changed to graphite ideal structure by disordered carbon, and (particle diameter D50 is 14.3 μm, and tap density is 1.04 g/cm after testing
3,specific area 2.9 ㎡/g), (particle diameter D50 is 11.3 μm, and tap density is 1.10 g/cm finally to add native graphite with the ratio of 1:0.1
3,specific area 1.6 ㎡/g) mix, finally obtain the negative material obtained by the present embodiment.
Embodiment 1 physical property detects as shown in table 1:
Table 1
Embodiment 2
With 100Kg native graphite " tailing " (particle diameter D50=2.31 μm, tap density 0.37 g/cm
3specific area 18.6 ㎡/g) be raw material, by weight graphite: pitch: the ratio of pore creating material=100:0.1:0.1, take the modified coal asphalt (softening point 150 DEG C) of 10Kg, the phenolic resins (softening point 110 DEG C) of 10Kg, put in the kneader with heater together, while mixing, kneader is warming up to 170 DEG C.Be mixed together 140min, then suppress with the material notice tablet press machine that kneading is good, improve its bulk density.By the material after compacting under inert gas shielding, rise to 950 DEG C with the heating rate of 5 DEG C/min, and be incubated one hour, be then cooled to room temperature.
Material after high temperature cabonization is by coarse crushing, shaping nodularization, and control the particle diameter Dmax of material, obtaining particle diameter D50 is 12.71 μm, and tap density is 0.94 g/cm
3,the powder of specific area 5.8 ㎡/g, then by high temperature graphitization (2800 DEG C) process, improve material property further, material internal structure is changed to graphite ideal structure by disordered carbon, and (particle diameter D50 is 12.27 μm, and tap density is 1.02 g/cm after testing
3,specific area 3.1 ㎡/g), (particle diameter D50 is 10.31 μm, and tap density is 1.10 g/cm finally to add native graphite with the ratio of 1:0.05
3,specific area 1.9 ㎡/g) mix, finally obtain the negative material obtained by the present embodiment.
Embodiment 2 physical property detects as shown in table 2:
Table 2
Embodiment 3
With 100Kg native graphite " tailing " (particle diameter D50=6.16 μm, tap density 0.59g/cm
3specific area 14.54 ㎡/g) be raw material, by weight graphite: pitch: the ratio of pore creating material=100:0.4:0.1, take the modified coal asphalt (softening point 100 DEG C) of 40Kg, the polyamide (softening point 80 DEG C) of 10Kg, put in the kneader with heater together, while mixing, kneader is warming up to 130 DEG C.Be mixed together 150min, then suppress with the material notice tablet press machine that kneading is good, improve its bulk density.By the material after compacting under inert gas shielding, rise to 1000 DEG C with the heating rate of 10 DEG C/min, and be incubated half an hour, be then cooled to room temperature.
Material after high temperature cabonization is by coarse crushing, shaping nodularization, and control the particle diameter Dmax of material, obtaining particle diameter D50 is 15.92 μm, and tap density is 0.93 g/cm
3,the powder of specific area 3.2 ㎡/g, then by high temperature graphitization (2600 DEG C) process, improve material property further, material internal structure is changed to graphite ideal structure by disordered carbon, and (particle diameter D50 is 15.35 μm, and tap density is 0.98g/cm after testing
3,specific area 2.7 ㎡/g), (particle diameter D50 is 11.3 μm, and tap density is 1.10 g/cm finally to add native graphite with the ratio of 1:0.09
3,specific area 1.6 ㎡/g) mix, finally obtain the negative material obtained by the present embodiment.
Embodiment 3 physical property detects as shown in table 3:
Table 3
Electrochemical property test
For the performance of negative material prepared by inspection the inventive method, test by half-cell method of testing, negative material with above embodiment and comparative example: acetylene black: PVDF(Kynoar)=93:3:4(weight ratio), add appropriate NMP(N-methyl pyrrolidone) furnishing pulpous state, coat on Copper Foil, within 8 hours, make negative plate through vacuum 110 DEG C of dryings; Be to electrode with metal lithium sheet, electrolyte is 1mol/L LiPF6/EC+DEC+DMC=1:1:1, and microporous polypropylene membrane is barrier film, is assembled into battery.Charging/discharging voltage is 0 ~ 2.0V, and charge-discharge velocity is 0.2C, and carry out testing to battery performance, test result is in table 4:
Table 4
In order to detect the high rate performance of negative material of the present invention in electrokinetic cell, adopting and being prepared into the detection that 4244130 type Soft Roll resultant battery carry out rate charge-discharge.
Negative material with embodiment and comparative example: SP:SBR(solid content 50%): CMC=94:2.5:1.5:2(weight ratio), add appropriate amount of deionized water and mix furnishing pulpous state, be applied on Copper Foil, at 90 DEG C, vacuumize drying; By LiFePO4 powder: SP:KS-6:PVDF=92:3.5:2:2.5(weight ratio), do after solvent evenly sizes mixing with NMP, be applied on aluminium foil, at 100 DEG C, vacuumize drying; By dried positive and negative electrode pole piece through roll-in, cut-parts, winding, fluid injection, sealing, formation process, make LiFePO4 power type 4244130 type Soft Roll resultant battery (nominal capacity is 2.5Ah), barrier film is Celgard2400, electrolyte is 1M LiPF6 ∕ DMC:EC:DEC, use powered cell detection device to carry out the detection of high rate performance, test result is in table 5:
Table 5
As from the foregoing, the material prepared by the present invention, various aspects of performance is excellent, can meet the index request of new-energy automobile power battery each side, have wide market prospects.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (8)
1. native graphite fine powder recycles the method as negative material, it is characterized in that, comprises following step:
Steps A: using " tailing " that produce in lithium battery natural graphite negative electrode material production process as raw material, add binding agent, pore creating material, at higher than asphalt softening point temperature 20 ~ 50 DEG C, carry out kneading granulation, then carry out roll-in or compacting, at high temperature 800 ~ 1000 DEG C, carry out carbonization;
Step B: the material after carbonization was entered pulverizing, shaping nodularization, obtains the spherical or oval graphite composite powder meeting particle size range requirement; More than 2600 DEG C, carry out high temperature graphitization, can " tailing " collected in pulverizing/nodularization process be added to steps A simultaneously and use as feedstock circulation;
Step C: carry out granularity allocation to the powder after graphitization processing, adds a certain proportion of modified natural graphite negative pole powder, is filled into the gap between particle, improves its bulk density by the mode of physical mixed.
2. the method for claim 1, is characterized in that, the particle diameter D50 of described raw material is 1 ~ 7 μm; Tap density≤0.6g/cm3, specific area >=10 ㎡/g.
3. the method for claim 1, is characterized in that, in described steps A, binding agent adopts modified coal tar pitch, and described modified coal tar pitch adopts one or more in coal tar pitch, petroleum asphalt, mesophase pitch, modified coal tar pitch.
4. the method for claim 1, is characterized in that, in described steps A pore creating material be phenolic resins, epoxy resin, polyvinyl alcohol, Corvic, polyamide one or more.
5. the method for claim 1, is characterized in that, graphite in described steps A: binding agent: the weight ratio of pore creating material is 100:0.1 ~ 0.4:0.01 ~ 0.1.
6. the method for claim 1, is characterized in that, the powder average grain diameter D50 obtained after pulverizing, shaping nodularization in described step B is 8 ~ 25 μm, Dmax≤55.
7. the method for claim 1, it is characterized in that, granularity allocation in described step C, the weight ratio of the graphite after carbonization and the graphite composite powder of interpolation is 1:0.05 ~ 0.2, wherein, the modified natural graphite negative pole diameter of particle of interpolation is less than the powder obtained after pulverizing, shaping nodularization in step B.
8. the method for claim 1, is characterized in that, heating rate 1 ~ 10 DEG C/min in described steps A.
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Cited By (7)
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| WO2016169149A1 (en) * | 2015-04-24 | 2016-10-27 | 深圳市斯诺实业发展有限公司 | Recycling method for graphite fine powder to act as lithium ion battery negative electrode material |
| CN108110364A (en) * | 2017-12-27 | 2018-06-01 | 东莞鑫茂新能源技术有限公司 | A kind of lithium cell cathode material recoverying and utilizing method |
| CN110451501A (en) * | 2019-08-19 | 2019-11-15 | 上海昱瓴新能源科技有限公司 | Utilize the artificial plumbago negative pole material and preparation method thereof of graphite electrode nipple powder preparation |
| CN110536863A (en) * | 2017-02-08 | 2019-12-03 | 国家电气碳制品公司 | Carbon dust and preparation method thereof |
| WO2020125018A1 (en) * | 2018-12-17 | 2020-06-25 | 贝特瑞新材料集团股份有限公司 | Low expansion graphite negative electrode material and preparation method therefor, and lithium ion battery |
| CN113264773A (en) * | 2021-05-26 | 2021-08-17 | 葫芦岛市铭浩新能源材料有限公司 | Method for preparing lithium ion battery cathode raw material by regeneration |
| CN113782709A (en) * | 2021-08-30 | 2021-12-10 | 大连中比动力电池有限公司 | Graphite negative electrode material, preparation method, negative electrode plate and lithium ion battery |
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