CN101417794A - Production manufacturing method of high rate lithium ionic cell cathode F series material - Google Patents
Production manufacturing method of high rate lithium ionic cell cathode F series material Download PDFInfo
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- CN101417794A CN101417794A CNA200710156443XA CN200710156443A CN101417794A CN 101417794 A CN101417794 A CN 101417794A CN A200710156443X A CNA200710156443X A CN A200710156443XA CN 200710156443 A CN200710156443 A CN 200710156443A CN 101417794 A CN101417794 A CN 101417794A
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Abstract
The invention relates to a production method for high multiplying power lithium ion battery cathode F-series materials, which is characterized by comprises the following steps of: choosing refinery coke, pitch coke and coal tar pitch coke sequentially and mixing according to the weight proportion of 50 plus or minus 5: 30 plus or minus 5: 20 plus or minus 5, calcining at 1200-1400 DEG C; carrying out breaking, filtering, pressing, roasting, graphitizing and machining separation, doped nodularization and high temperature carbonizing treatment; processing into the materials with different appearances (layered, ellipse-like and suborbicular) and mixing and doping based on the proportion of 40-50: 20-30: 30; and finally obtaining the high quality carbon powder F. The method is characterized in that the material has plenty of nanometer millipores on the surface, irregular and orderly appearances, high specific capacity, long cycle life, safety and reliability. The technology method of the carbon powder F-series cathode material is simple, mature and stable. The successful development of the material can completely replace the method of using nanometer carbon material to lift capacity and control the cost in the limit of middle-end material, thus being applicable to popularizing and applying in lithium battery industry.
Description
Technical field
The present invention relates to be applied to the method for manufacturing technical field of heavy body, high magnification, the plain powder of power lithium-ion battery negative pole F series material charcoal.
Background technology
Lithium ion battery is a domestic and international store battery green power supply product in the present age, is widely used in the information telecommunications industry.With international development of productivity, the quick consumption of petroleum resources, the caused environmental issue of pollution that city great amount of fuel oil vehicle exhaust produces becomes increasingly conspicuous, be the real tail gas pollution that solves automobile, the cry of development zero release electric vehicle is more and more high, the power truck key of success is a battery, and lithium ion battery is the ideal source of power truck.The electriclocomotive of countries and regions such as present Japanese America and Europe exploitation has begun to use the lithium ion battery power supply.
At present, the price increase of battery industry positive electrode material, the battery cost increases, thereby on the basis of original cost, improve battery performance effectively and obtain effective profit margin, key is the performance that promotes the active substance specific storage of negative material, improves the capacity (reducing anodal consumption) of corresponding anodal and reduces cost.
And the negative material F that arrives involved in the present invention on the basis based on the M series material, adds specialist additive, under 2400~2800 ℃ of high temperature, makes the plain powder of charcoal top layer form nanometer charcoal hole, thereby increases the performance of active substance specific storage.The performance that has broken through domestic and international anodal specific storage can only reach about 142mAh/g, the theoretical value of the plain powder 372mAh/g of charcoal; And the positive pole that has surpassed natural graphite is brought into play 145mAh/g, negative pole 350mAh/g, reached cobalt acid lithium performance 149.5mAh/g first, the plain powder of high-end artificial graphite charcoal that the plain powder reversible capacity performance of charcoal 360mAh/g is above. (considerably beyond the theoretical value of 372mAh/g).
Compacted density is from original 1.6g/cm
3, bring up to 1.70g/cm
3More than;
Can replace fully to be used in and add the way that nano-carbon material promotes capacity in the negative material, the real in the world precedent that belongs to.
Its characteristic is compared with natural graphite, and the consistence, stability, security, circulation that no matter are material are a kind of high capacity materials that meets long circulation, high platform considerably beyond natural graphite.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method for manufacturing of high rate lithium ionic cell cathode F series material, it obtains the plain powder material of charcoal and has that high-quality and safety is reliable, high rate during charging-discharging good, have extended cycle life, and processing method is simple, mature and stable, aboundresources.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of method for manufacturing of high rate lithium ionic cell cathode F series material is characterized in that steps in sequence is:
(1) refinery coke, pitch coke, coal-tar pitch is burnt through selected, remove useless impurity;
(2) refinery coke, pitch coke, the burnt material of coal-tar pitch are added mid-temperature pitch 20~40% (is benchmark with burnt weight) with ratio 50 ± 5:30 ± 5:20 ± 5, stir 10~50 fens clock times and cross oil press compression moulding, 1200~1400 ℃ of following roastings, the time is 5~7 days, makes base mateiral again;
(3) the base mateiral adding mid-temperature pitch 20~40% with gained is a soaker, with base mateiral weight is benchmark, carrying out first time high pressure soaks roasting and coats, barometric point 8~10kPa, soak 7~9 hours roasting time, and then under 2600~3200 ℃ of temperature, carry out the high temperature graphitization first time, the time is 7~15 days, tries to achieve finished base mateiral;
(4) will carry out stage treatment through the finished base mateiral crusher in crushing of above operation;
(5) carry out levigate processing piecemeal with the carse, medium and small processing of airflow milling then; According to the working method of airflow milling, particle is worn into: the size range of D10 (8~12 μ m), d50 (15~25 μ m), D90 (28~55 μ m);
(6) respectively the shaping of finished base mateiral granularity is modified to three kinds of patterns of stratiform, class ellipse, similar round; They can adjust and obtain with the airflow milling complete processing;
(7) stratiform, class ellipse, three kinds of materials of similar round are carried out proportioning and mix stirring by 50~60:30~40:10~20 part by weight;
(8) (high, medium and low temperature pitch all can the material of last operation gained to be mixed pitch 15~30%, but with mid-temperature pitch for the most suitable), carry out high pressure and soak the roasting coating, barometric point 8~10kPa soaks 7~9 hours roasting time, and then carries out high temperature graphitization under 2000~3000 ℃ of temperature, its purpose is the nanometer micropore of coating layer formation at high temperature, time is 7~15 days, and cooling is come out of the stove, and draws the high-end negative material that forms the nano-sized carbon micropore at last.
Compared with prior art, the invention has the advantages that:
Obtain the plain powder F of charcoal and conventional carbon microballoon, common high purity graphite, the plain powder of common charcoal by present method, natural graphite coating comparative effectiveness is obvious, specifically sees attached list:
The plain powder F of charcoal product technology performance advantage
The indicator of product variety function | Common graphite | The plain powder of common charcoal | The plain powder F of charcoal | Natural graphite coats | Carbosphere MCMB | The plain powder F of charcoal |
Reversible specific capacity | 280 | >340 | ≥360 | 350 | 320 | The specific storage height |
MAh/g | ||||||
Efficient % first | 83 | 92 | 〉=93.5 | 〉=92 | 〉=93 | Efficient height first |
Cycle life (number of times) | 300 | 300~800 | 600~1000 | 200~400 | 300~800 | Have extended cycle life |
Discharge platform % | 43 | 48 | 60 | 50 | 48 | The discharge platform height |
High-rate performance (2C/0.2C) | Generally | Good | Good | Generally | Good | High-rate performance is good |
With the electrolytic solution intermiscibility | Good | Good | Good | Difference | Good | Mutually solvent with electrolytic solution |
Compacted density g/cm 3 | 1.4 | 1.6 | 1.72 | 1.6 | 1.45 | The compacted density height |
Safety performance | Generally | Generally | Good | Difference | Good | Safety performance is reliable |
Market value (ten thousand yuan/ton) | 1.5 | 5.5 | 12.0 | 15.0 | 22.5 | The cost performance height |
And processing method is simple, and is mature and stable, aboundresources.
Lithium ion in process of charging, Li
+Take off embedding from negative electrode and come out to enter into anode through electrolytic solution, negative pole is in rich lithium state, and positive pole is in poor lithium state, in lithium ion embedding people carbon dioxide process carbon electrode process, the lithium ion trapped electron, the compensation charge of electronics supplies to negative pole from external circuit, guarantees the charge balance of negative pole.Reversed reaction, Li take place during discharge
+Take off embedding from the negative pole utmost point and come out to enter into positive pole through electrolytic solution, promptly uncharged lithium electricity becomes Li in carbon
+The time, electronics enters into external circuit, and lithium ion migration also enters into negative electrode, and meanwhile the electronics that provides of external circuit is with the local reduction of oxide compound lattice, and the two forms cathodic current.In normal charge and discharge process, lithium ion is the interlayer embedding people of the oxide compound of the carbon material of laminate structure and laminate structure and deviate from, the general variation that only causes basal spacing, do not destroy crystalline structure, in charge and discharge process, the chemical structure of negative material is constant substantially, therefore, from the reversibility that discharges and recharges, the reaction of lithium ion should be a kind of ideal reversible reaction.
The plain powder F of charcoal series material refinery coke is that main starting material pass through 3000-3200 ℃ of high temperature graphitization in earlier stage, thereby improves degree of graphitization.The lithium cell specific storage is high more, and cycle life is long more, and stability is good more, and the battery charging and discharging rate is big more.
Equally, interlamellar spacing also depends on the degree of graphitization of carbon, and the degree of graphitization increase helps Li
+Diffusion.
The F series material adds the certain proportion additive in the second time before the high temperature, combines with doping by machinery, on above basis, adopts the technology that coats again, is made into the F primary material.With production technique such as three kinds of different-shapes and the even collocation of size granularity, in high-temperature process, when removing organic impurity, generate nanometer micropore with the high temperature cabonization device then at material surface by additive.Material shape is the class ball-type, because irregular circle can increase substantially (the pole piece compacted density 〉=1.72~1.80g/cm of compacted density in battery making processes
3) cycle life: 600~1000 all capability retentions are simplified high-end ion cathode material lithium technical process more than 85% greatly, and improve material specific capacity, improve cycle performance and processing characteristics.
Description of drawings
Fig. 1 is a particle size distribution figure;
Fig. 2 is a sem photograph;
Fig. 3 is a discharge curve;
Fig. 4 is cycle life figure;
Fig. 5 is high temperature performance figure.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Comparative example's 1
(1) refinery coke, pitch coke, coal-tar pitch is burnt through selected, remove the impurity that does not have purposes;
(2) refinery coke, pitch coke, the burnt material of coal-tar pitch are added mid-temperature pitch 20~40% with ratio 50:30:20, with burnt weight is benchmark, stirs 10~50 fens clock times and crosses oil press compression moulding, again 1200~1400 ℃ of following roastings, time is 1~2 day, tries to achieve base mateiral;
(3) the base mateiral adding mid-temperature pitch 20~40% with gained is a soaker, with base mateiral weight is benchmark, carrying out first time high pressure soaks roasting and coats, barometric point 8~10kPa, soak 7~9 hours roasting time, and then under 2200~2400 ℃ of temperature, carry out the high temperature graphitization first time, the time is 7~15 days, tries to achieve finished base mateiral;
(4) will carry out stage treatment through the finished base mateiral crusher in crushing of above operation;
(5) carry out levigate processing piecemeal with the carse, medium and small processing of airflow milling then; According to the working method of airflow milling, particle is worn into: the size range of D10 (5~15 μ m), D50 (15~25 μ m), D90 (28~55 μ m);
(6) be lamellated pattern with finished base mateiral;
(7) (high, medium and low temperature pitch all can the material of last operation gained to be mixed pitch 15~30%, but with mid-temperature pitch for the most suitable), carry out high pressure and soak the roasting coating, barometric point 8~10kPa, soak 7~9 hours roasting time, and then carry out high temperature graphitization under 2000~2200 ℃ of temperature, its purpose is that at high temperature coating layer forms nanometer micropore, time is 7~15 days, and cooling is come out of the stove.
The gained material carries out the physical and chemical index test, and except that granularity, other index is all undesirable.
Comparative example's 2
Its steps in sequence of the plain powder F of charcoal method for manufacturing is:
(1) refinery coke, pitch coke, coal-tar pitch is burnt through selected, remove the impurity that does not have purposes;
(2) refinery coke, pitch coke, the burnt material of coal-tar pitch are added mid-temperature pitch 20~40% with ratio 50:30:20, with burnt weight is benchmark, stirs 10~50 fens clock times and crosses oil press compression moulding, again 1200~1400 ℃ of following roastings, time is 1~2 day, tries to achieve base mateiral;
(3) the base mateiral adding mid-temperature pitch 20~40% with gained is a soaker, with base mateiral weight is benchmark, carry out sub-high pressure and soak the roasting coating, barometric point 8~10kPa, soak 7~9 hours roasting time, and then at 2200~2400 ℃ of the temperature descending first time of high temperature graphitization, the time is 7~15 days, tries to achieve finished base mateiral;
(4) will carry out stage treatment through the finished base mateiral crusher in crushing of above operation;
(5) carry out levigate processing piecemeal with the carse, medium and small processing of airflow milling then; According to the working method of airflow milling, particle is worn into: the size range of D10 (8~12 μ m), D50 (15~25 μ m), D90 (28~55 μ m);
(6) shaping of finished base mateiral granularity is modified to the pattern of class ellipse;
(7) (high, medium and low temperature pitch all can the material of last operation gained to be mixed pitch 15~30%, but with mid-temperature pitch for the most suitable), carry out high pressure and soak the roasting coating, barometric point 8~10kPa, soak 7~9 hours roasting time, and then carry out high temperature graphitization under 2200~2400 ℃ of temperature, its purpose is that at high temperature coating layer forms nanometer micropore, time is 7~15 days, and cooling is come out of the stove.
The gained material is carried out physical and chemical index test, specific surface area makes moderate progress; Carry out battery testing, capacity has much room for improvement, and compacted density is on the low side.
Comparative example's 3
Its steps in sequence of the plain powder F of charcoal method for manufacturing is:
(1) pass through refinery coke, pitch coke, coal-tar pitch Jiao selected; Remove the impurity that does not have purposes;
(2) refinery coke, pitch coke, the burnt material of coal-tar pitch are added mid-temperature pitch 20~40% with ratio 50:30:20, with burnt weight is benchmark, stirs 10~50 fens clock times and crosses oil press compression moulding, again 1200~1400 ℃ of following roastings, time is 1~2 day, tries to achieve base mateiral;
(3) the base mateiral adding mid-temperature pitch 20~40% with gained is a soaker, with base mateiral weight is benchmark, carrying out first time high pressure soaks roasting and coats, barometric point 8~10kPa, soak 7~9 hours roasting time, and then under 2400~2600 ℃ of temperature, carry out the high temperature graphitization first time, the time is 7~15 days, tries to achieve finished base mateiral;
(4) will carry out stage treatment through the finished base mateiral crusher in crushing of above operation;
(5) carry out levigate processing piecemeal with the carse, medium and small processing of airflow milling then; According to the working method of airflow milling, particle is worn into: the size range of D10 (8~12 μ m), D50 (15~25 μ m), D90 (28~55 μ m);
(6) shaping of finished base mateiral granularity is modified to the pattern of similar round;
(7) (high, medium and low temperature pitch all can the material of last operation gained to be mixed pitch 15~30%, but with mid-temperature pitch for the most suitable), carry out high pressure and soak the roasting coating, barometric point 8~10kPa, soak 7~9 hours roasting time, and then carry out high temperature graphitization under 2400~2600 ℃ of temperature, its purpose is that at high temperature coating layer forms nanometer micropore, time is 7~15 days, and cooling is come out of the stove.
Gained material compacted density, positive and negative electrode capacity all increase, but platform is not high.
Comparative example's 4
Its steps in sequence of the plain powder F of charcoal method for manufacturing is:
(1) pass through refinery coke, pitch coke, coal-tar pitch Jiao selected; Remove the impurity that does not have purposes;
(2) refinery coke, pitch coke, the burnt material of coal-tar pitch are added mid-temperature pitch 20~40% with ratio 50 ± 5:30 ± 5:20 ± 5, with burnt weight is benchmark, stirs 10~50 fens clock times and crosses oil press compression moulding, again 1200~1400 ℃ of following roastings, time is 3~5 days, tries to achieve base mateiral;
(3) the base mateiral adding mid-temperature pitch 20~40% with gained is a soaker, with base mateiral weight is benchmark, carrying out first time high pressure soaks roasting and coats, barometric point 8~10kPa, soak 7~9 hours roasting time, and then under 2600~2800 ℃ of temperature, carry out the high temperature graphitization first time, the time is 7~15 days, tries to achieve finished base mateiral;
(4) will carry out stage treatment through the finished base mateiral crusher in crushing of above operation;
(5) carry out levigate processing piecemeal with the carse, medium and small processing of airflow milling then; According to the working method of airflow milling, particle is worn into: the size range of D10 (8~12 μ m), D50 (15~25 μ m), D90 (28~55 μ m);
(6) respectively the shaping of finished base mateiral granularity is modified to three kinds of patterns of stratiform, class ellipse or similar round;
(7) stratiform, class ellipse or three kinds of materials of similar round are carried out proportioning and mix stirring by 50~60:30~40:10~20 part by weight;
(8) (high, medium and low temperature pitch all can the material of last operation gained to be mixed pitch 15~30%, but with mid-temperature pitch for the most suitable), carry out high pressure and soak the roasting coating, barometric point 8~10kPa, soak 7~9 hours roasting time, and then carry out high temperature graphitization under 2600~2800 ℃ of temperature, its purpose is that at high temperature coating layer forms nanometer micropore, time is 7~15 days, and cooling is come out of the stove.
Gained material physical and chemical index is all up to standard, but not well lifting of positive electrode capacity performance, the negative pole ratio will exceed 5~10mAh/g when setting.Substantially meet the requirement of high-performance lithium cell negative electrode material.
Most preferred embodiment 5
The plain powder F of charcoal produces making method, and its steps in sequence is:
(1) pass through refinery coke, pitch coke, coal-tar pitch Jiao selected; Remove the impurity that does not have purposes
(2) refinery coke, pitch coke, the burnt material of coal-tar pitch are added mid-temperature pitch 20~40% with ratio 50 ± 5:30 ± 5:20 ± 5, with burnt weight is benchmark, stirs 10~50 fens clock times and crosses oil press compression moulding, again 1200~1400 ℃ of following roastings, time is 5~7 days, tries to achieve base mateiral;
(3) the base mateiral adding mid-temperature pitch 20~40% with gained is a soaker, with base mateiral weight is benchmark, carrying out first time high pressure soaks roasting and coats, barometric point 8~10kPa, soak 7~9 hours roasting time, and then under 2800~3200 ℃ of temperature, carry out the high temperature graphitization first time, the time is 7~15 days, tries to achieve finished base mateiral;
(4) will carry out stage treatment through the finished base mateiral crusher in crushing of above operation;
(5) carry out levigate processing piecemeal with the carse, medium and small processing of airflow milling then; According to the working method of airflow milling, particle is worn into: the size range of D10 (8~12 μ m), D50 (15~25 μ m), D90 (28~55 μ m);
(6) respectively the shaping of finished base mateiral granularity is modified to three kinds of patterns of stratiform, class ellipse or similar round; Three kinds of patterns of stratiform, class ellipse or similar round see that figure illustrates, the particle main body section is stratiform, ellipticity or circle shape respectively, and periphery can have irregular pattern curve.
(7) stratiform, class ellipse or three kinds of materials of similar round are carried out proportioning and mix stirring by 50~60:30~40:10~20 part by weight;
(8) (high, medium and low temperature pitch all can the material of last operation gained to be mixed pitch 15~30%, but with mid-temperature pitch for the most suitable), carry out high pressure and soak the roasting coating, barometric point 8~10kPa, soak 7~9 hours roasting time, and then carry out high temperature graphitization under 2600~2800 ℃ of temperature, its purpose is that at high temperature coating layer forms nanometer micropore, time is 7~15 days, and cooling is come out of the stove.
By above operation, make material surface form nanometer micropore, improved the lithium storage content of material, make the security of material and stability reach the requirement that heavy body, high-multiplying-power battery are made.Even particle size distribution, pole piece is smooth during coating, and the positive and negative electrode capacity is brought into play incisively and vividly.Trial-produceing successfully of this material can replace the way of using nano-carbon material to promote capacity fully, and cost control is in middle-end material boundary.This material is once releasing the concern just be subjected to vast battery manufacturer.Concrete parameter is seen Fig. 1~5.
The size range technology meaning of D10 in the literary composition (8~12 μ m), D50 (15~25 μ m), D90 (28~55 μ m) is interpreted as: D10, D50, D90 represent the mass percent that product cut size is shared, the size of these expression products of 8~12 μ m, the μ m of unit (micron).
Per-cent is mass percent herein, except that make specified otherwise.
Claims (5)
1, a kind of method for manufacturing of high rate lithium ionic cell cathode F series material is characterized in that steps in sequence is:
(1) pass through refinery coke, pitch coke, coal-tar pitch Jiao selected;
(2) refinery coke, pitch coke, the burnt material of coal-tar pitch are added pitch 20~40% with ratio 50 ± 5:30 ± 5:20 ± 5, with burnt weight is benchmark, stirs 10~50 fens clock times and crosses oil press compression moulding, again 1200~1400 ℃ of following roastings, time is 5~7 days, tries to achieve base mateiral;
(3) the base mateiral adding pitch 20~40% with gained is soaker, with base mateiral weight is benchmark, carrying out first time high pressure soaks roasting and coats, barometric point 8~10kPa, soak 7~9 hours roasting time, and then under 2600~3200 ℃ of temperature, carry out the high temperature graphitization first time, the time is 7~15 days, tries to achieve finished base mateiral;
(4) will carry out stage treatment through the finished base mateiral crusher in crushing of above operation;
(5) carry out levigate processing piecemeal with the carse, medium and small processing of airflow milling then;
(6) the base mateiral granularity shaping of levigate processing is modified to three kinds of patterns of stratiform, class ellipse or similar round;
(7) with stratiform, class ellipse or three kinds of materials of similar round by 50~60: 30~40: 10~20 part by weight carry out proportioning and mix to stir;
(8) material of last operation gained is mixed pitch 15-30%, carry out high pressure and soak the roasting coating, barometric point 8~10kPa, soak 7~9 hours roasting time, and then under 2000~3000 ℃ of temperature, carry out high temperature graphitization, time is 7~15 days, and cooling is come out of the stove, and draws the negative material that forms the nano-sized carbon micropore at last.
2, the method for manufacturing of high rate lithium ionic cell cathode F series material according to claim 1 is characterized in that step (2) is 50:30:20 with refinery coke, pitch coke, the burnt material ratio of coal-tar pitch.
3,, it is characterized in that the shaping of the finished base mateiral granularity of step (6) is modified to three kinds of patterns of stratiform, class ellipse or similar round according to the method for manufacturing of the described high rate lithium ionic cell cathode F series material of claim 2;
4, the method for manufacturing of high rate lithium ionic cell cathode F series material according to claim 2 is characterized in that step (7) laminate, class ellipse, three kinds of materials of similar round carry out proportioning and mix stirring by the 55:35:15 part by weight.
5,, it is characterized in that pitch adopts mid-temperature pitch according to the method for manufacturing of any described high rate lithium ionic cell cathode F series material of claim of claim 1 to 4.
6,, it is characterized in that airflow milling wears into particle the size range of D10 (5~15 μ m), D50 (15~25 μ m), D90 (28~55 μ m) according to the method for manufacturing of any described high rate lithium ionic cell cathode F series material of claim of claim 1 to 4.
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CN102173409B (en) * | 2011-01-04 | 2013-08-28 | 兴和县鑫源碳素有限公司 | Preparation method for graphite carbon material |
CN102208615A (en) * | 2011-05-05 | 2011-10-05 | 钱承亮 | Method for preparing carbon-carbon composite lithium ion battery cathode material |
CN102208615B (en) * | 2011-05-05 | 2013-10-23 | 钱承亮 | Method for preparing carbon-carbon composite lithium ion battery cathode material |
KR20170048934A (en) * | 2015-10-27 | 2017-05-10 | 삼성에스디아이 주식회사 | Negative active material for rechargeable lithium battery, and rechargeable lithium battery including same |
KR102449847B1 (en) | 2015-10-27 | 2022-09-29 | 삼성에스디아이 주식회사 | Negative active material for rechargeable lithium battery, and rechargeable lithium battery including same |
CN108807861A (en) * | 2017-05-03 | 2018-11-13 | 安普瑞斯(南京)有限公司 | A kind of Si-C composite material and preparation method thereof for lithium ion battery |
CN108218429A (en) * | 2017-10-10 | 2018-06-29 | 中国矿业大学 | A kind of method that high purity graphite material is prepared using coal tar pitch as raw material |
CN113800912A (en) * | 2021-11-04 | 2021-12-17 | 大连宏光锂业股份有限公司 | High compaction rate type lithium ion battery cathode material and preparation method thereof |
CN114477162A (en) * | 2021-12-31 | 2022-05-13 | 惠州锂威新能源科技有限公司 | Preparation method of graphite negative electrode material, product and application thereof |
CN114477162B (en) * | 2021-12-31 | 2023-09-05 | 惠州锂威新能源科技有限公司 | Preparation method of graphite anode material, product and application thereof |
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