CN102931381A - Isotropous graphite secondary particle, and preparation method and use thereof - Google Patents
Isotropous graphite secondary particle, and preparation method and use thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of an isotropous graphite secondary particle. The preparation method comprises the following steps: 1, mixing initial carbon material particles with modified asphalt particles to obtain a powder mixture with the initial carbon material particles as a continuous phase and the modified asphalt particles as a dispersion phase; 2, carrying out hot isothermal pressing treatment of the powder mixture, and removing the initial carbon material particles unbonded by the modified asphalt to obtain an isotropous graphite secondary particle precursor; and 3, sequentially carrying out heat treatments comprising non-melting treatment, charring treatment and graphitization treatment of the isotropous graphite secondary particle precursor. The isotropous graphite secondary particle macroscopically has the isotropy, can maintain the specific mass capacity of a cathode material, and simultaneously solves problems comprising low compacted density of a graphite cathode material piece and large baking expansion rate after the compacting of the piece, so the specific volume capacity of a lithium ion battery is improved.
Description
Technical field
The present invention relates to a kind of isotropic graphite second particle and its production and use.
Background technology
Present commercial carbon material used as negative electrode of Li-ion battery mainly contains two kinds of native graphite and Delaniums.Owing to having the characteristics such as high charge/discharge capacity, good charge and discharge platform, raw material wide material sources, production cost be low, it is used widely.
Along with the continuous progress of graphite material at negative technology of preparing, its discharge capacity has reached or near LiC
6Theoretical value 372mAh/g.In order to prepare high-capacity lithium ion cell, in keeping prior art, under the prerequisite of lithium ion battery negative Carbon Materials specific discharge capacity, improve its volume and capacity ratio and become study hotspot.
As everyone knows, crystal structure of graphite is the superimposed accumulation of aspect, carbon atom in aspect is with very strong covalent bonds, and be with weak Van der Waals force combination at the interlayer carbon atom, therefore graphite crystal mechanics, electricity and thermal property have obvious anisotropy on microcosmic, and it is served negative effect as the graphite material band of lithium ion battery negative.
In comminution process, graphite material from the weak interlayer faults of graphite crystal adhesion, forms sheet, tabular, strip graphite granule easily.Prepare lithium ion battery negative with such graphite granule, in pole coating roll-in process, sheet, tabular, strip graphite granule form easily and are parallel to aligning of collector, in lithium ion battery repeated charge process, lithium ion enter and deviate from graphite crystal when inner the c-axis direction of graphite can produce larger strain, cause electrode structure to destroy, affect cycle performance.Graphite granule aligning of collector also cause lithium ion from graphite crystal enter and the path of deviating from elongated, make the fast charging and discharging performance variation.And the processing characteristics of such graphite cathode material is also poor, and main manifestations is that the baking bounce-back after the low and compacting of graphite cathode material compacted density is large, and the lithium ion battery volume and capacity ratio is reduced.
In order to address the above problem, CN1645653A has proposed to make up or fit together the method for making spherical or similar spherical composite graphite second particle by binding agent by several or a plurality of sheets or flat graphite second particle.
The method adds binding agent to sheet or flat graphite granule, through mixing or kneading, these sheets or flat graphite granule are bonded together, through 2800 ℃ of heat treatments, pulverize again, namely make the crystal aspect and arranged uneven sphere or similar spherical combination graphite second particle, etc.
In fact, this method can not effectively address the above problem.This is because sheet or flat graphite granule add binding agent, after mixing or kneading, can become a thickener, namely become the comparatively perfect Delanium agglomerate of crystal structure of graphite after 2800 ℃ of heat treatments, carry out again powder crushing process, it or the interlayer faults easily on the c-axis direction of crystal and again become the graphite granule of sheet or strip; And said sphere or class sphere, irrelevant with the technical process before the heat treatment, powder is processed through spheroidization can become sphere or class sphere.
CN 1851963A adopts after kneading, compression molding, the 2800 ℃ of heat treatment the again technique of powder crushing process.This method has just formed significantly graphite granule and aligns when compression molding, therefore, with such graphite material powder process make cathode of lithium battery the time, aforesaid " exfoliated graphite particles phenomenon " and the series of problems of initiation thus still can appear.
Therefore wish a kind of isotropic graphite second particle of exploitation, use it as lithium ion battery negative material, can not form in the roll-in process of electrode preparation and be parallel to aligning of collector, under the prerequisite of the specific discharge capacity that keeps the prior art graphite cathode material, baking bounce-back rate after raising negative material compacted density, the reduction compacting, thus the lithium ion battery volume and capacity ratio improved.
Compacting and the bounce-back of graphite cathode material in the negative plate preparation process relates to Mechanical Properties of Materials, i.e. the strain-stress relation of material.Elastomeric stress and strain is linear in elastic limit, is reversible for alternate stress.Graphite material is different from elastomer, and its stress and strain is non-linear relation, and along with the increase of stress, strain increases, even under very little effect of stress, also plastic deformation can occur.
And the baking bounce-back is also relevant with the graphite material thermal expansion character.Graphite crystal a direction of principal axis thermal coefficient of expansion is minimum near normal temperature, is being negative value below 400 ℃; Graphite crystal c-axis direction thermal coefficient of expansion in all temperature ranges, be on the occasion of.
This mechanical characteristic of plastic deformation can occur in graphite material under effect of stress, make negative plate can obtain compacted density; And the graphite material expanded by heating is the one of the main reasons of pole piece compacting baking bounce-back.Be orientated along pole piece if graphite cathode material is aforesaid exfoliated graphite particles, then pole piece thickness will increase after the baking.Can not recover about at room temperature baking bounce-back, can think the plastic deformation of graphite material under this stress of expanded by heating.
Summary of the invention
Technical problem to be solved by this invention has been to overcome easy formation of existing graphite granule and has been parallel to aligning of collector, in lithium ion battery repeated charge process, lithium ion enter and deviate from graphite crystal when inner the c-axis direction of graphite can produce larger strain, cause electrode structure to destroy, affect cycle performance, make the defective of fast charging and discharging performance variation, thereby a kind of isotropic graphite second particle and its production and use is provided.Has isotropism on the graphite second particle macroscopic view of the present invention, with this isotropic graphite second particle as lithium ion battery negative material, the specific discharge capacity that both can keep the graphite negative material of lithium ion battery of prior art, solve simultaneously the large problem of baking expansion rate after the low and compacting of graphite cathode material compacted density that graphite cathode material causes because of the graphite crystal anisotropy, thereby improve the volume and capacity ratio of lithium ion battery.
One of purpose of the present invention has been to provide a kind of preparation method of isotropic graphite second particle, and it may further comprise the steps:
(1) the carbon material primary particles is mixed with the modified coal tar pitch particle, obtaining a kind of described carbon material primary particles is that continuous phase, described modified coal tar pitch particle are the mixed powder of decentralized photo; In described mixed powder, the ratio of described carbon material primary particles volume and described modified coal tar pitch particle volume is more than or equal to 2.0; The softening point of described modified coal tar pitch preferably is 120～260 ℃ more than 110 ℃, and analyses coke number more than 55%;
(2) described mixed powder is carried out the static pressure such as temperature and process, then remove the carbon material primary particles that is not bondd by described modified coal tar pitch, obtain isotropic graphite second particle precursor;
(3) described isotropic graphite second particle precursor is carried out following heat treatment successively: melt processed not, charing processing and graphitization processing get final product.
Has isotropism on the graphite second particle macroscopic view that is made by the inventive method.
In the step (1), described mixed powder is that described carbon material primary particles is continuous phase, described modified coal tar pitch particle is the mixed powder of decentralized photo, and namely described modified coal tar pitch particle is present among the encirclement of described carbon material primary particles with the state of discontinuous distribution.
In the step (1), the carbon material in the described carbon material primary particles can and/or can change into the material of Delanium for graphite through heat treatment.Described graphite can be Delanium and/or native graphite, and the described material that can change into Delanium through heat treatment preferably comprises coke and/or coal.Among the present invention, described native graphite and Delanium can be selected native graphite and the Delanium of all size in this area.
In the step (1), the average grain diameter of described carbon material primary particles can be selected according to the expection average grain diameter of described isotropic graphite second particle, preferably is 0.2～20 μ m.
In the step (1), described modified coal tar pitch is that pitch obtains through behind the heat polymerization, when it is lower than 110 ℃ when softening point, is unfavorable for pitch is made powder particle; When analysing coke number when being lower than 55%, the structural strength of graphite second particle will be affected; Therefore select softening point more than 110 ℃ and analyse coke number at the modified coal tar pitch more than 55% among the present invention.Described modified coal tar pitch particle average grain diameter is less on the average grain diameter impact of final isotropic graphite second particle, because in the process of described mixed powder being carried out the processing of the static pressure such as temperature, described modified coal tar pitch particle is bonded together carbon material primary particles on every side and forms isotropic graphite second particle precursor.At this moment described modified coal tar pitch particle is to become the skeleton structure in isotropic graphite second particle precursor and no longer be graininess with network-like or film-form.The size of described modified coal tar pitch particle average grain diameter has certain impact to the structural strength of final isotropic graphite second particle but simultaneously.Particle diameter too hour easily makes final isotropic graphite second particle structural strength on the low side, in the roll-in process of making negative plate, may destroy the structure of isotropic graphite second particle thus, thus the isotropism of losing; When particle diameter is excessive, when carrying out step (2), then may cause the adhesion of a plurality of isotropic graphite second particle precursors.Therefore, the average grain diameter of modified coal tar pitch particle is generally 10～1000 μ m among the present invention, is preferably 20～500 μ m, more preferably is 50～200 μ m.
In the step (1), in described mixed powder, described carbon material primary particles and described modified coal tar pitch particle are mixed by volume.The volume ratio of described carbon material primary particles and described modified coal tar pitch particle preferably is 2.0～25 more than or equal to 2.0, more preferably is 3～15, is 5～10 best.If it is continuous phase that this volume ratio, might can not get the carbon material primary particles less than 2.0, the modified coal tar pitch particle is the mixed powder of decentralized photo.
In the step (1), described mixing gets final product as continuous phase, described modified coal tar pitch particle as the mixed powder of decentralized photo to obtain a kind of described carbon material primary particles.
In the step (1), also can add this area graphitization catalyst commonly used in the described mixed powder, such as Fe
2O
3, SiO
2, SiC and B
4Among the C etc. one or more.The addition of described graphitization catalyst preferably is 0.1～20% of described carbon material primary particles and described modified coal tar pitch particle total weight.
In the step (2), the treatment temperature that the static pressure such as described temperature are processed is generally 60 ℃～450 ℃, is preferably 80 ℃～300 ℃.The processing pressure that the static pressure such as described temperature are processed is generally 20MPa～300MPa, is preferably 60MPa～200MPa.The processing time that the static pressure such as described temperature are processed is generally 0.1～10 hour.With regard to prior art, when being higher than the about 1.5 times temperature of its softening point, just has good caking property as the pitch of binding agent, and modified coal tar pitch of the present invention is under the temperature and pressure that the static pressure such as this temperature are processed acts on simultaneously, even during near the asphalt softening point temperature, the described modified coal tar pitch of processing through heat polymerization still can be bonded together the carbon material primary particles securely in treatment temperature.The static pressure such as described temperature are processed the quiet devices such as temperature that device therefor can be based on pascal's principle, also can adopt other plant equipment that can reach effect same, do not do particular determination among the present invention.
In the step (2), some carbon material primary particles and described modified coal tar pitch particle have formed isotropic graphite second particle precursor, rather than all mixed powders become an isotropic block integral body.Therefore, need just can obtain described isotropic graphite second particle precursor after the unnecessary carbon material primary particles of removal.The method of the described carbon material primary particles that described removal is not bondd by described modified coal tar pitch can adopt this area conventional method to carry out, such as classification or sieve.With the method for classification, the powder of removing less than isotropic graphite second particle precursor average grain diameter gets final product.Described sieving preferably is with 80 orders～270 purpose screen clothes, and the powder of removing under the sieve gets final product.
In the step (3), described not melt processed adopts vapour phase oxidation process to carry out, and its concrete operation method is: under 200～400 ℃ hot-air atmosphere, described isotropic graphite second particle precursor kept getting final product in 1～20 hour in 200～400 ℃.Described not melt processed is carried out in fluid bed.In described not melt processed, described modified coal tar pitch remains solid state, is infusible rotten pitch thereby make described modified coal tar pitch deep conversion.Like this, make described isotropic graphite second particle precursor in carbonization process, realize the solid phase charing of modified coal tar pitch, thereby the shape of isotropic graphite second particle precursor granules is not changed.
In the step (3), described charing processing or graphitization processing adopt this area conventional method to carry out, and the temperature that described charing is processed can be the conventional charing treatment temperature of this area, preferably is 800 ℃～1300 ℃.The time that described charing is processed can be the conventional charing processing time of this area, is preferably 1 hour～100 hours.The temperature of described graphitization processing can be the conventional graphitization processing temperature of this area, preferably is 2500 ℃～3200 ℃.The time of described graphitization processing can be the graphitization processing time of this area routine, is preferably 10 hours～200 hours.
Two of purpose of the present invention has been to provide a kind of isotropic graphite second particle that is made by said method.Isotropic graphite second particle of the present invention mainly is to be constituted by some small carbon material primary particles unordered (non orientation).Although graphite crystal has obvious anisotropy, the graphite second particle that some small unordered combining of carbon material primary particles are made with regard to its second particle, is isotropic on the macroscopic view.The present invention adopts the method for measuring two different directions resistivity of graphite second particle formed body to weigh its degree of isotropy, and the anisotropy ratio of its resistivity is 0.9～1.1.The measurement result of resistivity only is used for investigating the degree of isotropy of isotropic graphite second particle of the present invention, and it measures numerical value not as other performance judgment foundations.
The average grain diameter of the isotropic graphite second particle described in the present invention is not particularly limited, and can select according to actual needs.When the isotropic graphite second particle of the present invention during as lithium ion battery negative material, according to the manufacturing dimension requirement that the anticathode material proposes when the battery design of lithium ion battery manufacturing enterprise, the average particle diameter is at 5～50 μ m, and average grain diameter commonly used is at 10～25 μ m.
In isotropic graphite second particle of the present invention, the Fe constituent content is preferably below 25ppm.
Three of purpose of the present invention has been to provide the purposes of described isotropic graphite second particle as lithium ion battery negative material, but the purposes of isotropic graphite second particle of the present invention only is not limited to as lithium ion battery negative material, with isotropic graphite second particle raw material of the present invention, can also prepare isotropic graphite structure (bulk) material that the fields such as optical fiber production, monocrystalline silicon production, spark machined are used.
Among the present invention, but above-mentioned optimum condition combination in any on the basis that meets this area general knowledge namely gets each preferred embodiment of the present invention.
Raw material of the present invention and reagent is commercially available getting all.
Positive progressive effect of the present invention is:
1, be isotropic on the graphite second particle macroscopic view of the present invention, prepare lithium ion battery negative with isotropic graphite second particle of the present invention, graphite granule can not form and be parallel to aligning of collector in coating roll-in process, shorten lithium ion from the path that graphite crystal enters and deviates from, be conducive to improve the lithium ion battery fast charging and discharging performance.
2, graphite second particle of the present invention is as lithium ion battery negative material, the chemical property that both can keep the graphite cathode material that prior art makes, can significantly improve again the use compacted density of graphite cathode material, significantly reduce the baking bounce-back rate of graphite cathode material, thereby improve the volume and capacity ratio of lithium ion battery.
3, preparation method's technique of the present invention is simple, is easy to produce, and after the graphite second particle precursor graphitization processing, no longer through reprocessings such as pulverizing or abrasive dusts, is not easy to sneak into impurity.
Embodiment
The below further specifies the present invention with embodiment, but the present invention is not limited, and the raw material among the embodiment is conventional commercially available prod.
The raw material sources of the use among the following embodiment are:
Acicular petroleum coke powder U.S. big lake company
Petroleum coke powder Daqing petrochemical parent company
Coke-oven plant, pitch coke powder Huludao City
The coal measures modified coal tar pitch Zhenjiang auxiliary material of new light metallurgy factory
Flakey natural graphite powder Heilungkiang space graphite difficult to understand Co., Ltd
Electricity is forged (burning) anthracite Wuhai City Bo Hai charcoal and is have limit company
Embodiment 1
Raw material: acicular petroleum coke powder, average grain diameter 3～5 μ m; Coal measures modified coal tar pitch particle, average grain diameter 90～94 μ m, 135～145 ℃ of softening points are analysed coke number 55～65%; Fe
2O
3, average grain diameter is 3 μ m.
Preparation method: with 10 parts of (volume) acicular petroleum coke powder, 2 parts of (volume) coal measures modified coal tar pitch particles and 6wt%Fe
2O
3(take acicular petroleum coke powder and coal measures modified coal tar pitch particle total weight as radix) at room temperature mixed 40 minutes, and obtaining the acicular petroleum coke powder is continuous phase, and coal measures modified coal tar pitch particle is the mixed powder of decentralized photo; With the described mixed powder mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 120 ℃, temperature waits static pressure to process 30 minutes under the 80MPa pressure, taking-up is cooled to room temperature, remove the unnecessary acicular petroleum coke powder as the carbon material primary particles with gas flow sizing machine, obtain isotropic graphite second particle precursor; Described isotropic graphite second particle precursor placed pass into 320 ℃ of hot-airs in the fluid bed, melt processed is 10 hours, then carries out 1100 ℃ charing 20 hours, in 2900 ℃ of graphitization processing 80 hours, obtains isotropic graphite second particle.Its physicochemical property is listed in table 1.
The method of testing of resistivity is: 75 parts (weight ratio) isotropic graphite second particle is mixed with 25 parts of (weight ratio) binding agents, and making bulk density by the press compression molding is 1.35g/cm
3The sample piece, and 95 ℃ of lower curing 10 hours, then measure respectively the resistivity of the parallel moulding pressure direction of sample piece and vertical forming pressure direction, calculate anisotropy ratio.
With described isotropic graphite second particle as negative material, processing characteristics---the compacted density (g/cm under each pressure when measuring it and making negative plate
3), baking under the different compacted density (95 ℃, the bounce-back rate after 6h), the result lists in table 2 and the table 3 respectively.
Make button cell with described isotropic graphite second particle as negative material, carry out the correlated performance test.Manufacturing process and the testing procedure of button cell are as follows:
The negative material of 100 weight portions and the conductive carbon black of 2 weight portions are joined in the binder solution (the N-methyl-pyrrolidone solution of 6wt% Kynoar) of 120 weight portions; stir; then coating, dry, compressing tablet; cut the pole piece of diameter 16mm; accurately weighing; drying is 4 hours in 110 ℃ vacuum drying chamber, take lithium metal as to the utmost point, is assembled into button cell CR2430 in the glove box (water and oxygen content are controlled at below the 3ppm) of argon shield.
Barrier film: Celgard 2400 porous polypropylene films.
Electrolyte: the EC/DMC/EMC of 1.0mol/L LiPF6 (volume ratio 1: 1: 1) solution.
Battery testing:
Adopt the Q/TEZI01-2010 standard this battery to be tested test result such as table 1.
Embodiment 2
Raw material: acicular petroleum coke powder, average grain diameter 3～5 μ m; Coal measures modified coal tar pitch particle, average grain diameter 90～94 μ m, 135～145 ℃ of softening points are analysed coke number 55～65%; Fe
2O
3, average grain diameter is 3 μ m.
Preparation method: with 10 parts of (volume) acicular petroleum coke powder, 2 parts of (volume) coal measures modified coal tar pitch particles and 6wt%Fe
2O
3(take petroleum coke powder and coal measures modified coal tar pitch particle total weight as radix) at room temperature mixed 40 minutes, and obtaining the acicular petroleum coke powder is continuous phase, and coal measures modified coal tar pitch particle is the mixed powder of decentralized photo; With the described mixed powder mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 80 ℃, temperature waits static pressure to process 30 minutes under the 80MPa pressure, taking-up is cooled to room temperature, remove the unnecessary acicular petroleum coke powder as the carbon material primary particles with gas flow sizing machine, obtain isotropic graphite second particle precursor; Described isotropic graphite second particle precursor placed pass into 320 ℃ of hot-airs in the fluid bed, melt processed was 10 hours, then carries out 1100 ℃ charing 20 hours, in 2900 ℃ of graphitization processing 80 hours, obtain isotropic graphite second particle, its physicochemical property is listed in table 1.Compacted density (g/cm under each pressure
3), baking under the different compacted density (95 ℃, the bounce-back rate after 6h), the result lists in table 2 and the table 3 respectively.Its correlated performance test and method thereof are with embodiment 1.
Embodiment 3
Raw material: acicular petroleum coke powder, average grain diameter 3～5 μ m; Coal measures modified coal tar pitch particle, average grain diameter 90～94 μ m, 135～145 ℃ of softening points are analysed coke number 55～65%; Fe
2O
3, average grain diameter is 3 μ m.
Preparation method: with 10 parts of (volume) acicular petroleum coke powder, 2 parts of (volume) coal measures modified coal tar pitch particles and 6wt%Fe
2O
3(take acicular petroleum coke powder and coal measures modified coal tar pitch particle total weight as radix) at room temperature mixed 40 minutes, and obtaining the acicular petroleum coke powder is continuous phase, and coal measures modified coal tar pitch particle is the mixed powder of decentralized photo; With the described mixed powder mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 300 ℃, temperature waits static pressure to process 30 minutes under the 80MPa pressure, taking-up is cooled to room temperature, remove the unnecessary acicular petroleum coke powder as the carbon material primary particles with gas flow sizing machine, obtain isotropic graphite second particle precursor; Described isotropic graphite second particle precursor placed pass into 320 ℃ of hot-airs in the fluid bed, melt processed was 10 hours, then carries out 1100 ℃ charing 20 hours, in 2900 ℃ of graphitization processing 80 hours, obtain isotropic graphite second particle, its physicochemical property is listed in table 1.Compacted density (g/cm under each pressure
3), baking under the different compacted density (95 ℃, the bounce-back rate after 6h), the result lists in table 2 and the table 3 respectively.Its correlated performance test and method thereof are with embodiment 1.
Embodiment 4
Raw material: flakey natural graphite powder, average grain diameter 3～5 μ m; Coal measures modified coal tar pitch particle, average grain diameter 90～94 μ m, 135～145 ℃ of softening points are analysed coke number 55～65%.
Preparation method: 10 parts of (volume) flakey natural graphite powders, 2 parts of (volume) coal measures modified coal tar pitch particles (take flakey natural graphite powder and coal measures modified coal tar pitch particle total weight as radix) were at room temperature mixed 40 minutes, obtaining the flakey natural graphite powder is continuous phase, and coal measures modified coal tar pitch particle is the mixed powder of decentralized photo; With the described mixed powder mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 120 ℃, temperature waits static pressure to process 30 minutes under the 80MPa pressure, taking-up is cooled to room temperature, remove the unnecessary flakey natural graphite powder as the carbon material primary particles with gas flow sizing machine, obtain isotropic graphite second particle precursor; Described isotropic graphite second particle precursor placed pass into 320 ℃ of hot-airs in the fluid bed, melt processed was 10 hours, then carries out 1100 ℃ charing 20 hours, in 2900 ℃ of graphitization processing 80 hours, obtain isotropic graphite second particle, its physicochemical property is listed in table 1.Compacted density (g/cm under each pressure
3), baking under the different compacted density (95 ℃, the bounce-back rate after 6h), the result lists in table 2 and the table 3 respectively.Its correlated performance test and method thereof are with embodiment 1.
Embodiment 5
Raw material: petroleum coke powder, average grain diameter 3～5 μ m; Coal measures modified coal tar pitch particle, average grain diameter 90～100 μ m, 135～145 ℃ of softening points are analysed coke number 55～65%; Fe
2O
3, average grain diameter is 3 μ m.
Preparation method: with 10 parts of (volume) petroleum coke powders, 2 parts of (volume) coal measures modified coal tar pitch particles and 6wt%Fe
2O
3(take petroleum coke powder and coal measures modified coal tar pitch particle total weight as radix) at room temperature mixed 40 minutes, and obtaining petroleum coke powder is continuous phase, and coal measures modified coal tar pitch particle is the mixed powder of decentralized photo; With the described mixed powder mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 120 ℃, temperature waits static pressure to process 30 minutes under the 80MPa pressure, taking-up is cooled to room temperature, remove the unnecessary petroleum coke powder as the carbon material primary particles with gas flow sizing machine, obtain isotropic graphite second particle precursor; Described isotropic graphite second particle precursor placed pass into 320 ℃ of hot-airs in the fluid bed, melt processed is 10 hours, then carry out 1100 ℃ charing 20 hours, in 2900 ℃ of graphitization processing 120 hours, obtain isotropic graphite second particle, its physicochemical property is listed in the table 1, and other test results are listed in respectively table 1～table 3.Its correlated performance test and method thereof are with embodiment 1.
Embodiment 6
Raw material: pitch coke powder, average grain diameter 3～5 μ m; Coal measures modified coal tar pitch particle, average grain diameter 90～100 μ m, 135～145 ℃ of softening points are analysed coke number 55～65%; Fe
2O
3, average grain diameter is 3 μ m.
Preparation method: with 10 parts of (volume) pitch coke powders, 2 parts of (volume) coal measures modified coal tar pitch particles and 15wt%Fe
2O
3(take pitch coke powder and coal measures modified coal tar pitch particle total weight as radix) at room temperature mixed 40 minutes, and obtaining the pitch coke powder is continuous phase, and coal measures modified coal tar pitch particle is the mixed powder of decentralized photo; With the described mixed powder mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 120 ℃, temperature waits static pressure to process 30 minutes under the 80MPa pressure, taking-up is cooled to room temperature, remove the unnecessary pitch coke powder as the carbon material primary particles with gas flow sizing machine, obtain isotropic graphite second particle precursor; Described isotropic graphite second particle precursor placed pass into 320 ℃ of hot-airs in the fluid bed, melt processed is 10 hours, then carry out 1100 ℃ charing 20 hours, in 2900 ℃ of graphitization processing 150 hours, obtain isotropic graphite second particle, its physicochemical property is listed in the table 1, and other test results are listed in respectively table 1～table 3.Its correlated performance test and method thereof are with embodiment 1.
Embodiment 7
Raw material: pitch coke powder, petroleum coke powder, average grain diameter 3～5 μ m; Coal measures modified coal tar pitch particle, average grain diameter 90～100 μ m, 135～145 ℃ of softening points are analysed coke number 55～65%; Fe
2O
3, average grain diameter is 3 μ m.
Preparation method: with 7 parts of (volume) petroleum coke powders, 3 parts of (volume) modified coal tar pitch coke powders, 2 parts of (volume) coal measures modified coal tar pitch particles and 6wt%Fe
2O
3(take petroleum coke powder, pitch coke powder and coal measures modified coal tar pitch particle total weight as radix) at room temperature mixed 40 minutes, and obtaining pitch coke powder and petroleum coke powder is continuous phase, and coal measures modified coal tar pitch particle is the mixed powder of decentralized photo; With the described mixed powder mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 120 ℃, temperature waits static pressure to process 30 minutes under the 80MPa pressure, taking-up is cooled to room temperature, remove unnecessary pitch coke powder and petroleum coke powder as the carbon material primary particles with gas flow sizing machine, obtain isotropic graphite second particle precursor (d50 ≈ 23 μ m); Described isotropic graphite second particle precursor placed pass into 320 ℃ of hot-airs in the fluid bed, melt processed is 10 hours, then carry out 1100 ℃ charing 20 hours, in 2900 ℃ of graphitization processing 80 hours, obtain isotropic graphite second particle, its physicochemical property is listed in the table 1, and other test results are listed in respectively table 1～table 3.Its correlated performance test and method thereof are with embodiment 1.
Embodiment 8
Raw material: acicular petroleum coke powder, average grain diameter 0.2～0.5 μ m; The electric calcined anthracite powder, average grain diameter 2～5 μ m; Coal measures modified coal tar pitch particle, average grain diameter 850～855 μ m, 180～200 ℃ of softening points are analysed coke number 70～80%; Fe
2O
3, average grain diameter is 3 μ m.
Preparation method: with 9 parts of (volume) acicular petroleum coke powder, 1 part of (volume) electric calcined anthracite powder, 0.4 part of (volume) coal measures modified coal tar pitch particle and 6wt%Fe
2O
3(take acicular petroleum coke powder, electric calcined anthracite powder and coal measures modified coal tar pitch particle total weight as radix) at room temperature mixed 40 minutes, and obtaining acicular petroleum coke powder and electric calcined anthracite powder is continuous phase, and coal measures modified coal tar pitch particle is the mixed powder of decentralized photo; With the described mixed powder mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 450 ℃, temperature waits static pressure to process 12 minutes under the 20MPa pressure, taking-up is cooled to room temperature, remove unnecessary acicular petroleum coke powder and electric calcined anthracite powder as the carbon material primary particles with gas flow sizing machine, obtain isotropic graphite second particle precursor (d50 ≈ 16 μ m); Described isotropic graphite second particle precursor placed pass into 320 ℃ of hot-airs in the fluid bed, melt processed is 10 hours, then carry out 1100 ℃ charing 20 hours, in 2900 ℃ of graphitization processing 80 hours, obtain isotropic graphite second particle, its physicochemical property is listed in table 1, and other test results are listed in respectively table 1～table 3.Its correlated performance test and method thereof are with embodiment 1.
Embodiment 9
Raw material: acicular petroleum coke powder, average grain diameter 1.8～2.0 μ m; Coal measures modified coal tar pitch particle, average grain diameter 200～205 μ m, 160～180 ℃ of softening points are analysed coke number 65～75%; SiO
2, average grain diameter is 3 μ m.
Preparation method: with 10 parts of (volume) acicular petroleum coke powder, 1 part of (volume) coal measures modified coal tar pitch particle and 8wt%SiO
2(take acicular petroleum coke powder and coal measures modified coal tar pitch particle total weight as radix) at room temperature mixed 40 minutes, and obtaining the acicular petroleum coke powder is continuous phase, and coal measures modified coal tar pitch particle is the mixed powder of decentralized photo; With the described mixed powder mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 240 ℃, temperature waits static pressure to process 20 minutes under the 50MPa pressure, taking-up is cooled to room temperature, remove the unnecessary acicular petroleum coke powder as the carbon material primary particles with gas flow sizing machine, obtain isotropic graphite second particle precursor (d50 ≈ 19 μ m); Described isotropic graphite second particle precursor placed pass into 320 ℃ of hot-airs in the fluid bed, melt processed is 10 hours, then carries out 1100 ℃ charing 20 hours, in 2900 ℃ of graphitization processing 80 hours, obtains isotropic graphite second particle.Its physicochemical property is listed in table 1, and other test results are listed in respectively table 1～table 3.Its correlated performance test and method thereof are with embodiment 1.
Embodiment 10
Raw material: acicular petroleum coke powder, average grain diameter 8～10 μ m; Coal measures modified coal tar pitch particle, average grain diameter 45～50 μ m, 135～145 ℃ of softening points are analysed coke number 55～65%; B
4C, average grain diameter is 3 μ m.
Preparation method: with 10 parts of (volume) acicular petroleum coke powder, 3 parts of (volume) coal measures modified coal tar pitch particles and 5wt%B
4C (take acicular petroleum coke powder and coal measures modified coal tar pitch particle total weight as radix) at room temperature mixed 40 minutes, and obtaining the acicular petroleum coke powder is continuous phase, and coal measures modified coal tar pitch particle is the mixed powder of decentralized photo; With the described mixed powder mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 80 ℃, temperature waits static pressure to process 4 hours under the 300MPa pressure, taking-up is cooled to room temperature, remove the unnecessary acicular petroleum coke powder as the carbon material primary particles with gas flow sizing machine, obtain isotropic graphite second particle precursor (d50 ≈ 21 μ m); Described isotropic graphite second particle precursor placed pass into 320 ℃ of hot-airs in the fluid bed, melt processed is 10 hours, then carries out 1100 ℃ charing 20 hours, in 2900 ℃ of graphitization processing 80 hours, obtains isotropic graphite second particle.Its physicochemical property is listed in table 1, and other test results are listed in respectively table 1～table 3.Its correlated performance test and method thereof are with embodiment 1.
Embodiment 11
Raw material: acicular petroleum coke powder, average grain diameter 16～18 μ m; Coal measures modified coal tar pitch particle, average grain diameter 10～15 μ m, 135～145 ℃ of softening points are analysed coke number 55～65%; SiC, average grain diameter is 5 μ m.
Preparation method: 10 parts of (volume) acicular petroleum coke powder, 5 parts of (volume) coal measures modified coal tar pitch particles and 7wt%SiC (take acicular petroleum coke powder and coal measures modified coal tar pitch particle total weight as radix) were at room temperature mixed 40 minutes, obtaining the acicular petroleum coke powder is continuous phase, and coal measures modified coal tar pitch particle is the mixed powder of decentralized photo; With the described mixed powder mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 60 ℃, temperature waits static pressure to process 8 hours under the 300MPa pressure, taking-up is cooled to room temperature, remove the unnecessary acicular petroleum coke powder as the carbon material primary particles with gas flow sizing machine, obtain isotropic graphite second particle precursor; Described isotropic graphite second particle precursor placed pass into 320 ℃ of hot-airs in the fluid bed, melt processed is 10 hours, then carries out 1100 ℃ charing 20 hours, in 2900 ℃ of graphitization processing 80 hours, obtains isotropic graphite second particle.Its physicochemical property is listed in table 1, and other test results are listed in respectively table 1～table 3.Its correlated performance test and method thereof are with embodiment 1.
The comparative example 1
Raw material: acicular petroleum coke powder, average grain diameter 3～5 μ m; Coal measures modified coal tar pitch particle, average grain diameter 90～100 μ m; 135～145 ℃ of softening points are analysed coke number 55～65%; Fe
2O
3, average grain diameter is 3 μ m.
Preparation method: the Fe that gets 56 parts of (weight) acicular petroleum coke powder, 44 parts of (weight) coal measures modified coal tar pitch particles, 6wt%
2O
3(take acicular petroleum coke grain weight amount as radix) was 230 ℃ of lower kneadings 90 minutes; With this kneading thing mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 120 ℃, temperature waits static pressure to process taking-up in 30 minutes under the 80MPa pressure, carry out 1000 ℃～1200 ℃ charings 20 hours, then 2800 ℃～3000 ℃ graphitization processing 80 hours make the graphite second particle by pulverizing.This graphite second particle is carried out the test identical with embodiment 1, the results are shown in table 1～table 3.Its correlated performance test and method thereof are with embodiment 1.
The comparative example 2
Raw material: petroleum coke powder, average grain diameter 3～5 μ m; Coal measures modified coal tar pitch particle, average grain diameter 90～100 μ m, 135～145 ℃ of softening points are analysed coke number 55～65%; Fe
2O
3, average grain diameter is 3 μ m.
Preparation method: the Fe that gets 56 (weight) part petroleum coke powder, 44 parts of (weight) coal measures modified coal tar pitch particles, 6wt%
2O
3(take petroleum coke powder weight as radix) was 230 ℃ of lower kneadings 90 minutes; With this kneading thing mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 120 ℃, temperature waits static pressure to process to take out in 30 minutes under the 80MPa pressure; This petroleum coke powder and coal measures modified coal tar pitch kneading thing are carried out 1000 ℃～1200 ℃ charings 20 hours, and then 2800 ℃～3000 ℃ graphitization processing 80 hours make the graphite second particle by pulverizing.This graphite second particle is carried out the test identical with embodiment 1, the results are shown in table 1～table 3.Its correlated performance test and method thereof are with embodiment 1.
The comparative example 3
Raw material: pitch coke powder, average grain diameter 3～5 μ m; Coal measures modified coal tar pitch particle, average grain diameter 90～100 μ m, 135～145 ℃ of softening points are analysed coke number 55～65%; Fe
2O
3, average grain diameter is 3 μ m.
Preparation method: the Fe that gets 56 parts of (weight) pitch coke powders, 44 parts of (weight) coal measures modified coal tar pitch particles, 6wt%
2O
3(take pitch coke grain weight amount as radix) was 230 ℃ of lower kneadings 90 minutes; With this kneading thing mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 120 ℃, temperature waits static pressure to process to take out in 30 minutes under the 80MPa pressure; Carry out 1000 ℃～1200 ℃ charings 20 hours, then 2800 ℃～3000 ℃ graphitization processing 80 hours make the graphite second particle by pulverizing.This graphite second particle is carried out the test identical with embodiment 1, the results are shown in table 1～table 3.Its correlated performance test and method thereof are with embodiment 1.
The comparative example 4
Raw material: pitch coke powder, petroleum coke powder, average grain diameter 3～5 μ m; Coal measures modified coal tar pitch particle, average grain diameter 60～65 μ m, 135～145 ℃ of softening points are analysed coke number 55～65%; Fe
2O
3, average grain diameter is 3 μ m.
Preparation method: get 39 parts of (weight) petroleum coke powders, 17 parts of (weight) pitch coke powders, 44 parts of (weight) coal measures modified coal tar pitch particles, 6wt%Fe
2O
3(take pitch coke powder and petroleum coke powder total weight as radix); 230 ℃ of lower kneadings 90 minutes; With this kneading thing mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 120 ℃, temperature waits static pressure to process taking-up in 30 minutes under the 80MPa pressure, carry out 1000 ℃～1200 ℃ charings 20 hours, then 2800 ℃～3000 ℃ graphitization processing 80 hours make the graphite second particle by pulverizing.This graphite second particle is carried out the test identical with embodiment 1, the results are shown in table 1～table 3.Its correlated performance test and method thereof are with embodiment 1.
The comparative example 5
Raw material: flakey natural graphite powder, average grain diameter 3～5 μ m; Coal measures modified coal tar pitch particle, average grain diameter 90～100 μ m, 135～145 ℃ of softening points are analysed coke number 55～65%.
Preparation method: get 56 parts of (weight) flakey natural graphite powders, 44 parts of (weight) coal measures modified coal tar pitches (take pitch coke grain weight amount as radix), 230 ℃ of lower kneadings 90 minutes; With this kneading thing mould of packing into, by KJYW255-450 type temperature isostatic pressing machine, at 120 ℃, temperature waits static pressure to process to take out in 30 minutes under the 80MPa pressure; Carry out 1000 ℃～1200 ℃ charings 20 hours, then 2800 ℃～3000 ℃ graphitization processing 80 hours make the graphite second particle by pulverizing.This graphite second particle is carried out the test identical with embodiment 1, the results are shown in table 1～table 3.Its correlated performance test and method thereof are with embodiment 1.
Table 1
Table 2
Table 3
Shown by table 1 test result, embodiment 1-11 and comparative example 1-5 chemical property first discharge capacity, be in peer-level aspect the discharging efficiency first; Aspect tap density, embodiment 1-11 is apparently higher than comparative example 1-5, mean height 25%; The anisotropy ratio test result shows that embodiment 1-11 is isotropic graphite, and comparative example 1-5 is obvious anisotropy.
Experimental result by table 2 shows that the compacted density of embodiment 1-11 embodiment under each listed pressure of table 2 all is significantly higher than each comparative example.
Experimental result by table 3 shows that under roughly the same compacted density, embodiment 1-11 baking bounce-back rate all is starkly lower than corresponding comparative example 1-5, and is particularly evident under high compacted density.
In sum, the present invention has kept the chemical property of the graphite cathode material of prior art; Aspect the powder key property, the present invention also obviously shows the graphite cathode material that is better than prior art; Particularly the processing characteristics of graphite cathode material is compared with the graphite cathode material of prior art, and the present invention has significantly improved the compacted density of graphite cathode material, has significantly reduced the baking bounce-back rate of graphite cathode material simultaneously.
It is as shown in table 4 to the present invention relates to test event, instrument or method of testing.
Table 4
Claims (12)
1. the preparation method of an isotropic graphite second particle, it is characterized in that: it may further comprise the steps:
(1) the carbon material primary particles is mixed with the modified coal tar pitch particle, getting a kind of described carbon material primary particles is that continuous phase, described modified coal tar pitch particle are the mixed powder of decentralized photo; In described mixed powder, the volume ratio of described carbon material primary particles and described modified coal tar pitch particle is more than or equal to 2.0; The softening point of described modified coal tar pitch is 120～260 ℃ preferably more than 110 ℃, analyses coke number more than 55%;
(2) described mixed powder is carried out the static pressure such as temperature and process, then remove the described carbon material primary particles that is not bondd by described modified coal tar pitch, obtain isotropic graphite second particle precursor;
(3) described isotropic graphite second particle precursor is carried out following heat treatment successively: melt processed not, charing processing and graphitization processing get final product.
2. the preparation method of isotropic graphite second particle as claimed in claim 1, it is characterized in that: in the step (1), the carbon material in the described carbon material primary particles is graphite and/or the material that can change into Delanium through heat treatment; Described graphite is preferably Delanium and/or native graphite, and the described material that can change into Delanium through heat treatment preferably comprises coke and/or coal.
3. the preparation method of isotropic graphite second particle as claimed in claim 1 or 2, it is characterized in that: in the step (1), the average grain diameter of described carbon material primary particles is 0.2～20 μ m.
4. the preparation method of isotropic graphite second particle as claimed in claim 1, it is characterized in that: in the step (1), the average grain diameter of described modified coal tar pitch particle is 10～1000 μ m, preferably is 20～500 μ m, more preferably is 50～200 μ m.
5. such as the preparation method of each described isotropic graphite second particle in the claim 1～4, it is characterized in that: the volume ratio of described carbon material primary particles and described modified coal tar pitch particle is 2.0～25, preferably being 3～15, more preferably is 5～10.
6. such as the preparation method of each described isotropic graphite second particle in the claim 1～5, it is characterized in that: in the step (1), also add graphitization catalyst in the described mixed powder; Described graphitization catalyst preferably is Fe
2O
3, SiO
2, SiC and B
4Among the C one or more; The addition of described graphitization catalyst preferably is 0.1～20% of described carbon material primary particles and described modified coal tar pitch particle total weight.
7. the preparation method of isotropic graphite second particle as claimed in claim 1 is characterized in that: in the step (2), the treatment temperature that the static pressure such as described temperature are processed is 60 ℃～450 ℃, preferably is 80 ℃～300 ℃; The processing pressure that the static pressure such as described temperature are processed is 20MPa～300MPa, preferably is 60MPa～200MPa; The processing time of the static pressure such as described temperature is 0.1～10 hour.
8. the preparation method of isotropic graphite second particle as claimed in claim 1 is characterized in that: the method for the described carbon material primary particles that described removal is not bondd by described modified coal tar pitch is classification or sieves; Described sieving preferably is with 80 orders～270 purpose screen clothes, and the powder of removing under the sieve gets final product.
9. the preparation method of isotropic graphite second particle as claimed in claim 1, it is characterized in that: in the step (3), described not melt processed adopts vapour phase oxidation process to carry out, its concrete operation method is: under 200～400 ℃ hot-air atmosphere, described isotropic graphite second particle precursor kept getting final product in 1～20 hour in 200～400 ℃.
10. the preparation method of isotropic graphite second particle as claimed in claim 1 is characterized in that: in the step (3), the temperature that described charing is processed is 800 ℃～1300 ℃; The time that described charing is processed is 1 hour～100 hours; The temperature of described graphitization processing is 2500 ℃～3200 ℃, and the time of described graphitization processing is 10 hours～200 hours.
11. the isotropic graphite second particle that is made by the preparation method of each described isotropic graphite second particle in the claim 1～10; The average grain diameter of described isotropic graphite second particle preferably is 5～50 μ m, more preferably is 10～25 μ m; The anisotropy ratio of described isotropic graphite second particle resistivity is 0.9～1.1.
12. isotropic graphite second particle as claimed in claim 11 is as the application of lithium ion battery negative material.
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| CN113875037B (en) * | 2020-04-30 | 2023-08-04 | 宁德时代新能源科技股份有限公司 | Secondary battery, method for manufacturing the same, and device comprising the same |
| CN114873589A (en) * | 2022-05-30 | 2022-08-09 | 乌海宝杰新能源材料有限公司 | High-compaction-density high-rate-performance graphite negative electrode material and preparation method thereof |
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Effective date of registration: 20190902 Address after: 014020 Neimenggu Autonomous Region Baotou Qingshan District Equipment Manufacturing Industrial Park New Planning District Management Committee A Block 312, 313, 314, 315 Patentee after: INNER MONGOLIA SHANSHAN TECHNOLOGY Co.,Ltd. Address before: 3177 Jucai Road, Wangchun Industrial Park, Yinzhou District, Ningbo City, Zhejiang Province Co-patentee before: SHANGHAI SHANSHAN TECH Co.,Ltd. Patentee before: NINGBO SHANSHAN NEW MATERIAL TECH Co.,Ltd. |
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Denomination of invention: An isotropic graphite secondary particle and its preparation method and Application Effective date of registration: 20220701 Granted publication date: 20160720 Pledgee: Baotou Branch of Inner Mongolia Hohhot Jingu Rural Commercial Bank Co.,Ltd. Pledgor: INNER MONGOLIA SHANSHAN TECHNOLOGY Co.,Ltd. Registration number: Y2022150000063 |