CN105098184A - Preparation method of composite graphite, composite graphite and lithium ion battery - Google Patents
Preparation method of composite graphite, composite graphite and lithium ion battery Download PDFInfo
- Publication number
- CN105098184A CN105098184A CN201510621926.7A CN201510621926A CN105098184A CN 105098184 A CN105098184 A CN 105098184A CN 201510621926 A CN201510621926 A CN 201510621926A CN 105098184 A CN105098184 A CN 105098184A
- Authority
- CN
- China
- Prior art keywords
- coke
- ultra
- green
- composite graphite
- carbon dust
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a preparation method of composite graphite to overcome the problems that the composite graphite prepared by the method in the prior art is low in energy density, poor in high-rate charge and discharge properties and high in expansion rate in the charging and discharging processes. The preparation method comprises the following steps: (S1) providing ultrafine carbon powder, wherein the ultrafine carbon powder comprises green coke and/or mesophase carbon green microspheres; (S2) mixing the ultrafine carbon powder with a binder to obtain a mixture A, mixing the mixture A with a catalyst to obtain a mixture B, and then carrying out combined treatment on the mixture B to obtain a precursor; (S3) carrying out graphitizing treatment on the precursor to obtain a semi-finished product; and (S4) crushing, spheroidizing, wrapping and sieving the semi-finished product to obtain the composite graphite. Meanwhile, the invention further discloses the composite graphite prepared by the method and a lithium ion battery. The composite graphite provided by the invention is high in energy density, good in liquid absorption and retention properties, good in isotropic property, good in high-rate charge and discharge properties and low expansion rate in the charging and discharging processes.
Description
Technical field
The preparation method that the present invention relates to a kind of composite graphite and the composite graphite prepared by the method, and comprise the lithium ion battery of this composite graphite.
Background technology
In recent years with the development of mobile communication and mancarried electronic aid, have higher requirement to providing the performance of lithium ion battery of the energy.Negative material has significant impact to performance of lithium ion battery, in existing negative material, the novel high-capacity negative pole such as Si base, Sn base and Al base slowly can not get applying because of its cost and technical factor, and conventional graphite class negative material will continue leading negative pole market because of features such as its stable performance, technology maturation, cost are low within a period of time.
Current graphite negative electrodes actual capacity, close to theoretical capacity, further improves energy density per unit volume metric density when mass-energy density metric density is constant, is one of possible improvement direction.Well-known graphite granule meeting genetic horizon spacing in removal lithium embedded process changes and SEI film thickens, and then causes cathode pole piece expansion, SEI film rupture even active material stripping and barrier film fracture, affects cycle performance and security performance.The battery performance caused that expands to prevent cathode pole piece worsens, and mainly adopts the way of reserved pole piece expansion space in battery design at present, and the method cannot solve pole piece expansion issues from basic, also limit the lifting of energy density.
Take i Phone as the digital communication equipment development of new generation of representative, make the slow problem of graphite cathode charging rate day by day become the serious problems affecting Consumer's Experience.
In order to solve the problem, patent CN1645653A proposes burnt to sheet or tabular class particle to be combined into by binding agent has spherical or class spherical precursor, and then graphitization obtains the method for compound temper carbon particle, this second particle has macroscopically isotropic.
In actual production, burnt class particle and binding agent associativity poor, finished product sphericity is lower, and pulverizing of easily breaking in fragmentation after graphitization and spheroidizing process, becomes anisotropic sheet or tabular graphite granule again.
Anisotropic graphite raw material obtain after average grain diameter is the superfine graphite powder of 2-10 μm by pulverizing, classification, screening process by patent CN103811758A, again by secondary granulation technical finesse, improve the isotropism of graphite granule and the end face/basal plane ratio of graphite granule, thus improve the high rate during charging-discharging of material volumetric expansion blockage effect and material in doff lithium process.
The program is raw materials used is Delanium or native graphite, and cost of material is high, graphite and binding agent adhesion poor, needed for compound, binding agent ratio is high, limit the further raising of tap density and specific capacity, only improve embedding lithium speed from isotropism angle, high rate performance improves limited.
The mixture of powdered carbon, binding agent and catalyst is added thermal agitation by patent CN103855369A, compressing, charing, graphitization.
It is low to there is finished product specific capacity in the program, the problem that first effect is low, compacted density is low.
The needle coke of optimized proportion, same sex Jiao, native graphite mix by patent CN103682347A, mixture material is placed in graphitizing furnace and carries out graphitization purification process, final obtained ion secondary battery cathode material lithium, further shaping, classification, screening are carried out to the powder after graphitization, obtain composite lithium ion battery cathode material.
The performance of the graphite granule that the method prepares improves limited, and cannot improve orientation.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method of composite graphite, the composite graphite that the method prepares have that energy density is high, imbibition water retainability is good, isotropic behavior good, large multiplying power charge and discharge performance is good, expansion rate is low in charge and discharge process feature.
It is as follows that the present invention solves the problems of the technologies described above adopted technical scheme:
A kind of preparation method of composite graphite is provided, it is characterized in that, comprise the steps:
S1, provide ultra-fine carbon dust; Described ultra-fine carbon dust comprises green coke and/or carbonaceous mesophase spherules green-ball;
S2, ultra-fine carbon dust to be mixed with binding agent, obtain mixture A, mixture A and catalyst mix, obtain mixture B, then Combined Processing is carried out to mixture B, obtain presoma;
S3, graphitization processing is carried out to presoma, obtain semi-finished product;
S4, semi-finished product are pulverized, spheroidization, coated, screening, obtain described composite graphite.
Meanwhile, present invention also offers a kind of composite graphite prepared by said method.
In addition, present invention also offers a kind of lithium ion battery, comprise positive pole stacked successively, barrier film and negative pole; Described negative pole comprises negative current collector and is positioned at the negative material on described negative current collector, and described negative material comprises foregoing composite graphite.
In the preparation method of composite graphite provided by the invention, containing green coke and/or carbonaceous mesophase spherules green-ball in the raw material adopted, make full use of green coke or carbonaceous mesophase spherules green-ball stickiness, reduce binding agent use amount, be conducive to reducing costs, improving jolt ramming, compacted density and specific capacity.Further, add catalyst and carry out Combined Processing in green coke, catalyst can partly enter green coke granule interior, and catalytic action is more even, catalyst utilization is higher.
Meanwhile, the present invention, by ultra-fine carbon dust to be mixed rear Combined Processing with binding agent, realizes ultra-fine carbon dust secondary granulation, is conducive to improving isotropic behavior, is conducive to improving high rate performance and reducing pole piece expansion rate.
Adding of ultra-fine carbon dust secondary granulation and catalyst, improve porosity, improve imbibition water retainability, improve high rate charge-discharge performance; Reprocessing adopts spheroidization and cladding process, compensate for second particle jolt ramming, head imitates shortcoming on the low side.
In addition, the present invention, by isotropism particle and anisotropic particle compound, both provided more Lithium-ion embeding passages, in turn ensure that the specific capacity of finished product, compacting.
The composite graphite that method disclosed by the invention prepares first specific capacity is greater than 360mAg/g, and efficiency is greater than 95% first, and pole piece compaction density is greater than 1.75g/cc.Its outstanding feature is that porosity is higher, imbibition water retainability is good, isotropic behavior good, large multiplying power charge and discharge performance is good, expansion rate is low in charge and discharge process.To lithium battery improve further energy density, shorten the charging interval have positive effect.
Accompanying drawing explanation
Fig. 1 is the high rate performance resolution chart of the lithium ion battery that the composite graphite adopting embodiment of the present invention 1-6 and comparative example 1-2 to prepare respectively prepares;
Fig. 2 is the SEM figure of the composite graphite that embodiment 6 provided by the invention prepares.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The preparation method of composite graphite provided by the invention comprises the steps:
S1, provide ultra-fine carbon dust; Described ultra-fine carbon dust comprises green coke and/or carbonaceous mesophase spherules green-ball;
S2, ultra-fine carbon dust to be mixed with binding agent, obtain mixture A, mixture A and catalyst mix, obtain mixture B, then Combined Processing is carried out to mixture B, obtain presoma;
S3, graphitization processing is carried out to presoma, obtain semi-finished product;
S4, semi-finished product are pulverized, spheroidization, coated, screening, obtain described composite graphite.
According to the present invention, at least containing green coke and/or carbonaceous mesophase spherules green-ball in above-mentioned ultra-fine carbon dust.Wherein, green coke can adopt one or more in the burnt green coke of Raw needle coke, pitch coke green coke, the same sex.
In the present invention, by preparing composite graphite on the ultra-fine carbon dust basis containing green coke and/or carbonaceous mesophase spherules green-ball, green coke stickiness can be made full use of, reducing binding agent use amount, being conducive to reducing costs, improving jolt ramming, compacted density and specific capacity.
Concrete, above-mentioned ultra-fine carbon dust can comprise various carbon materials, such as, specifically can comprise one or more in needle coke, pitch coke, same sex Jiao, native graphite, Delanium, carbonaceous mesophase spherules green-ball.
Above-mentioned needle coke is Raw needle coke and/or ripe Jiao of needle coke; Described pitch coke is pitch coke green coke and/or ripe Jiao of pitch coke; Described same sex Jiao is the burnt green coke of the same sex and/or burnt ripe Jiao of the same sex.
In the present invention, under preferable case, the fugitive constituent of above-mentioned various green coke is 5-40%.According to above-mentioned various ripe Jiao, its fugitive constituent is less than 5%.Under further preferable case, the needle coke adopted in above-mentioned ultra-fine carbon dust, pitch coke, same sex Jiao are green coke, and its fugitive constituent is 5-20%.
For above-mentioned needle coke, preferably its ash content is less than 0.5%.Burnt for the above-mentioned same sex, preferably its degree of crystallinity is less than 30%.
Understandable, when above-mentioned needle coke be needle coke ripe burnt time, must green coke containing other kinds or carbonaceous mesophase spherules green-ball in ultra-fine carbon dust.It is the burnt situation for burnt ripe Jiao of the same sex of ripe Jiao of pitch coke or the same sex that same situation is applicable to pitch coke.On the contrary, if in ultra-fine carbon dust without carbonaceous mesophase spherules green-ball time, then must containing at least one in above-mentioned green coke.
In the present invention, under preferable case, above-mentioned ultra-fine carbon dust comprises that native graphite, needle coke, the same sex are burnt, one or more in carbonaceous mesophase spherules green-ball.Under further preferable case, in mass ratio, native graphite content is below 70wt%, and needle coke content is below 70wt%, and the burnt content of the same sex is below 30wt%, and carbonaceous mesophase spherules green-ball content is below 70wt%.More preferably in situation, containing the micro crystal graphite accounting for ultra-fine carbon dust total weight 0-10wt% in above-mentioned native graphite.
Same sex Jiao can provide more Lithium-ion embeding passages, but its capacity is on the low side.Carbonaceous mesophase spherules can provide more Lithium-ion embeding passages, and capacity is high, but its cost is higher.The capacity of needle coke is high, circulate, but its high rate performance is poor.And native graphite can improve capacity and compacted density, but its high rate performance and cycle performance poor.
In the present invention by by above-mentioned plurality of raw materials with the use of, isotropism particle (such as same sex Jiao or carbonaceous mesophase spherules green-ball) and anisotropic particle (such as native graphite or needle coke) compound, more Lithium-ion embeding passages were both provided, in turn ensure that the specific capacity of finished product, compacting, and there is excellent cycle performance and high rate performance.
According to the present invention, under preferable case, in above-mentioned ultra-fine carbon dust, native graphite and Raw needle coke weight sum are 70-90wt%, and the burnt green coke content of the same sex is 10-30wt%.
Or carbonaceous mesophase spherules green-ball and native graphite weight sum are greater than 50wt%, the burnt green coke content of the same sex is less than 20wt%, and burnt ripe Jiao of the same sex and/or needle coke content are less than 30wt%.
Preferred, green coke and carbonaceous mesophase spherules green-ball total weight proportion are 50-70wt%, and native graphite ratio is 30-50wt%, and ripe coke ratio example is less than 20%.Wherein, the ratio that carbonaceous mesophase spherules green-ball ratio accounts for ultra-fine carbon dust total weight is greater than 30wt%.
According to the present invention, under preferable case, the D of above-mentioned ultra-fine carbon dust
50for 2-10 μm, more preferably 7-8 μm.
In the present invention, above-mentioned ultra-fine carbon dust directly can buy the various material powders meeting above-mentioned condition, obtains after mixing.Also convenient source can be adopted to prepare, such as, obtain the various raw materials of required proportioning, then mix, through pulverizing, classification, screening, spheroidization, obtain ultra-fine carbon dust.According to actual conditions, under preferable case, the D of the ultra-fine carbon dust obtained after spheroidization
50for 2-10 μm.
The concrete technology step and method of above-mentioned pulverizing, classification, screening, spheroidization is known in the field, repeats no more in the present invention.
As described in step S2, after obtaining above-mentioned ultra-fine carbon dust, also comprise and ultra-fine carbon dust is mixed with binding agent, obtain mixture A, mixture A and catalyst mix, obtain mixture B.
Above-mentioned binding agent can adopt various binding agents conventional in prior art, such as, and one or more in specifically can adopting in soft pitch, phenolic resins, epoxy resin, mylar or polyamide.As is known in the art, when above-mentioned binding agent in use, as the case may be, first can adopt organic solvent dissolution, and then mix.
In the present invention, under preferable case, soft pitch during above-mentioned binding agent adopts.Above-mentioned middle soft pitch can adopt coal measures or oil system pitch.More preferably, in situation, the softening point of described middle soft pitch is 50-100 DEG C.
According to the present invention, as previously mentioned, owing to containing green coke and/or carbonaceous mesophase spherules green-ball in ultra-fine carbon dust, only the binding agent of less content need be adopted can to prepare the product composite graphite of function admirable.Under preferable case, in described mixture B, the ratio that binder content accounts for ultra-fine carbon dust is less than 20wt%.
In said mixture B, catalyst can adopt conventional various catalyst, such as, can be selected from silicon, silicon compound, iron, iron compound, boron, boron compound one or more.In described mixture B, the ratio that catalyst content accounts for ultra-fine carbon dust is less than 30wt%.
In the present invention, under preferable case, described catalyst is silicon compound.In described mixture B, the ratio that catalyst content accounts for ultra-fine carbon dust is 5-20wt%.
As previously mentioned, containing green coke and/or carbonaceous mesophase spherules green-ball in above-mentioned ultra-fine carbon dust, add catalyst and after carrying out Combined Processing, catalyst can partly enter green coke granule interior, catalytic action more evenly, catalyst utilization is higher.Also can reduce the use amount of catalyst on the other hand, reduce costs.
According to the present invention, after obtaining said mixture B, Combined Processing need be carried out to mixture B, obtain presoma.
Concrete, described Combined Processing can adopt existing various compounding method, such as can be selected from solid phase kneading, liquid phase kneading, roll in sheet, fusion, spraying dry, mold pressing, isostatic pressed, carbonization one or more.
In the present invention, under preferable case, Combined Processing can comprise first carries out liquid phase kneading, and then mold pressing.Be more preferably, first liquid phase kneading carried out to mixture B, then carry out rolling sheet, mold pressing, isostatic pressed, carbonization treatment, obtain above-mentioned presoma.
For above-mentioned liquid phase kneading, under preferable case, its temperature is 100-300 DEG C, and the time is 1-2h.When binding agent adopt in soft pitch time, be more preferably soft pitch softening point height 50-90 DEG C in liquid phase kneading temperature ratio.
Because the present invention is by mixing rear Combined Processing with binding agent by ultra-fine carbon dust, realizing ultra-fine carbon dust secondary granulation, being conducive to improving isotropic behavior, be conducive to improving high rate performance and reducing pole piece expansion rate.
Adding of ultra-fine carbon dust secondary granulation and catalyst, improve porosity, improve imbibition water retainability, improve high rate charge-discharge performance; Reprocessing adopts spheroidization and cladding process, compensate for second particle jolt ramming, head imitates shortcoming on the low side.
According to the present invention, as step S3, graphitization processing need be carried out to presoma, obtain semi-finished product.Above-mentioned graphited process is known in the field.In the present invention, under preferable case, the temperature of described graphitization processing is 2700-3200 DEG C.
By above-mentioned graphitization processing, this finished product can be obtained.Finally, as step S4, semi-finished product are pulverized, spheroidization, coated, screening, obtain described composite graphite.
Concrete, first can carry out mechanical crushing, ball milling to semi-finished product, and then spheroidization.
Above-mentioned coated process specifically can adopt the one in the coated or mechanical fusion of conventional liquid phase, solid phase.The clad material that described coated process adopts be selected from pitch, resin, electrically conductive graphite one or more.Under preferable case, above-mentioned clad material is middle soft pitch and electrically conductive graphite, or resin and middle soft pitch.
According to the present invention, under preferable case, described coated process is liquid phase coating, after described liquid phase coating, also comprise carbonization treatment before screening process.
Above-mentioned carbonization treatment temperature is preferably 600-1500 DEG C.Described screen size D
50be preferably 4-30 μm.
Reprocessing of the present invention adopts spheroidization and cladding process, compensate for second particle jolt ramming, head imitates shortcoming on the low side.
Meanwhile, present invention also offers the composite graphite prepared by said method.
In addition, present invention also offers a kind of lithium ion battery, comprise positive pole stacked successively, barrier film and negative pole; Described negative pole comprises negative current collector and is positioned at the negative material on described negative current collector, and described negative material comprises foregoing composite graphite.
The material of lithium ion battery, structure and preparation method can adopt various method of the prior art, and the present invention repeats no more.
By the following examples the present invention is further detailed.
Embodiment 1
The present embodiment is for illustration of the preparation method of composite graphite disclosed by the invention.
Step 1, by burnt for same sex green coke and the ripe burnt raw material mixing of needle coke, mechanical crushing and air-flow is adopted to be crushed to D respectively
50for 4-5 μm, obtain ultra-fine carbon dust.
Step 2, by ultra-fine for step 1 gained carbon dust, according to the burnt green coke of the same sex: ripe Jiao of needle coke: di-iron trioxide=30:70:15 ratio adds kneading machine, be heated to 200 DEG C, according to mixture A dry powder: soft pitch=100:20 adds fusing soft pitch, after kneading 1h, compression molding is carried out in taking-up, obtains presoma.
Step 3, by block for step 2 gained presoma, carry out graphitization, obtain semi-finished product.
Step 4, step 3 gained semi-finished product are carried out Mechanical Crushing successively, screening, obtains D
50for the composite graphite finished product of 12-13 μm.
Gained physical and chemical indexes is in table 1, and high rate performance is shown in Fig. 1.
Embodiment 2
The present embodiment is for illustration of the preparation method of composite graphite disclosed by the invention.
Step 1, by ripe to burnt for the same sex green coke, Raw needle coke and needle coke burnt raw material mixing, mechanical crushing and air-flow is adopted to be crushed to D respectively
50for 4-5 μm, obtain ultra-fine carbon dust.
Step 2, by ultra-fine for step 1 gained carbon dust, according to the burnt green coke of the same sex: Raw needle coke: ripe Jiao of needle coke: diboron trioxide=30:40:30:15 ratio adds kneading machine, be heated to 200 DEG C, according to mixture A dry powder: soft pitch=100:10 adds fusing soft pitch, after carrying out kneading 1h, compression molding is carried out in taking-up, obtains presoma.
Step 3, by block for step 2 gained presoma, carry out graphitization, obtain semi-finished product.
Step 4, step 3 gained semi-finished product are carried out Mechanical Crushing successively, screening, obtains D
50for the composite graphite finished product of 12-13 μm.
Gained physical and chemical indexes is in table 1, and high rate performance is shown in Fig. 1.
Embodiment 3
The present embodiment is for illustration of the preparation method of composite graphite disclosed by the invention.
Step 1, by burnt for same sex green coke and the mixing of Raw needle coke raw material, mechanical crushing and air-flow is adopted to be crushed to D respectively
50for 4-5 μm, obtain ultra-fine carbon dust
Step 2, by ultra-fine for step 1 gained carbon dust, according to the burnt green coke of the same sex: Raw needle coke: diboron trioxide=30:70:15 ratio adds kneading machine, is heated to 200 DEG C, not adding additives, after carrying out kneading 1h, take out and carry out compression molding, obtain presoma.
Step 3, by block for step 2 gained presoma, carry out graphitization, obtain semi-finished product.
Step 4, step 3 gained semi-finished product are carried out Mechanical Crushing successively, screening, obtains D
50for the composite graphite finished product of 12-13 μm.
Gained physical and chemical indexes is in table 1, and high rate performance is shown in Fig. 1
Embodiment 4
The present embodiment is for illustration of the preparation method of composite graphite disclosed by the invention.
Step 1, by burnt for same sex green coke and the ripe burnt raw material mixing of needle coke, mechanical crushing and air-flow is adopted to be crushed to D
50for 4-5 μm, obtain ultra-fine carbon dust.
Step 2, by ultra-fine for step 1 gained carbon dust, according to the burnt green coke of the same sex: ripe Jiao of needle coke: di-iron trioxide=30:70:15 ratio adds kneading machine, be heated to 200 DEG C, according to mixture A dry powder: soft pitch=100:20 adds fusing soft pitch, after kneading 2h, taking-up is carried out rolling sheet, pulverizing, compression molding, obtains presoma.
Step 3, by block for step 2 gained presoma, carry out graphitization, graphitization temperature 3000 DEG C, time 14d, obtains semi-finished product.
Step 4, step 3 gained semi-finished product are carried out Mechanical Crushing, spheroidization successively, screening, obtains D
50for the composite graphite finished product of 12-13 μm.
Gained physical and chemical indexes is in table 1, and high rate performance is shown in Fig. 1
Embodiment 5
The present embodiment is for illustration of the preparation method of composite graphite disclosed by the invention.
Step 1, by Raw needle coke, the burnt green coke of the same sex and natural graphite starting material mixing, mechanical crushing and air-flow is adopted to be crushed to D
50for 7-8 μm, obtain ultra-fine carbon dust.
Step 2, by ultra-fine for step 1 gained carbon dust, according to the burnt green coke of the same sex: Raw needle coke: native graphite: carborundum=20:30:50:15 ratio adds kneading machine, be heated to 200 DEG C, according to mixture A dry powder: soft pitch=100:15 adds fusing soft pitch, after kneading 2h, taking-up is carried out rolling sheet, pulverizing, compression molding, obtains presoma.
Step 3, by block for step 2 gained presoma, carry out graphitization, graphitization temperature 3000 DEG C, time 14d, obtains semi-finished product.
Step 4, step 3 gained semi-finished product are carried out Mechanical Crushing, spheroidization successively, screening, D
50for the composite graphite finished product of 12-13 μm.
Gained physical and chemical indexes is in table 1, and high rate performance is shown in Fig. 1
Embodiment 6
The present embodiment is for illustration of the preparation method of composite graphite disclosed by the invention.
Step 1, Raw needle coke, carbonaceous mesophase spherules green-ball and natural graphite starting material to be mixed, adopt mechanical crushing and air-flow to be crushed to D
50for 7-8 μm, obtain ultra-fine carbon dust.
Step 2, by ultra-fine for step 1 gained carbon dust, according to carbonaceous mesophase spherules green-ball: Raw needle coke: native graphite: carborundum=40:20:30:10 ratio adds kneading machine, be heated to 200 DEG C, according to mixture A dry powder: soft pitch=100:5 adds fusing soft pitch, after kneading 2h, taking-up is carried out rolling sheet, pulverizing, compression molding, obtains presoma.
Step 3, by block for step 2 gained presoma, carry out graphitization, graphitization temperature 3000 DEG C, time 14d, obtains semi-finished product.
Step 4, step 3 gained semi-finished product are carried out Mechanical Crushing, spheroidization successively, solid phase method pitch-coating, covering amount is 1.5%, 1100 DEG C of carbonizations, and screening, obtains D
50for the composite graphite finished product of 12-13 μm.
Gained physical and chemical indexes is in table 1, and high rate performance is shown in Fig. 1, and SEM pattern is shown in Fig. 2
Comparative example 1
This comparative example is used for the preparation method of comparative illustration composite graphite disclosed by the invention.
Step 1, by burnt for the same sex ripe Jiao and the ripe burnt raw material mixing of needle coke, mechanical crushing and air-flow is adopted to be crushed to D respectively
50for 4-5 μm, obtain ultra-fine carbon dust.
Step 2, by ultra-fine for step 1 gained carbon dust, according to burnt ripe Jiao of the same sex: ripe Jiao of needle coke: carborundum=30:70:15 ratio adds kneading machine, be heated to 200 DEG C, according to mixture A dry powder: soft pitch=100:40 adds fusing soft pitch, after kneading 1h, compression molding is carried out in taking-up, obtains presoma.
Step 3, by block for step 2 gained presoma, carry out graphitization, obtain semi-finished product.
Step 4, step 3 gained semi-finished product are carried out Mechanical Crushing successively, screening, obtains D
50for the composite graphite finished product of 12-13 μm.
Gained physical and chemical indexes is in table 1, and high rate performance is shown in Fig. 1
Comparative example 2
This comparative example is used for the preparation method of comparative illustration composite graphite disclosed by the invention.
Step 1, by burnt to native graphite and the same sex ripe Jiao, the ripe Jiao's mixing of needle coke, adopt mechanical crushing and air-flow to be crushed to D50=3-5 μm, obtain ultra-fine carbon dust.
Step 2, by ultra-fine for step 1 gained carbon dust, according to burnt ripe Jiao of the same sex: ripe Jiao of needle coke: native graphite: carborundum=50:20:30:15 ratio adds kneading machine, be heated to 200 DEG C, according to mixture A dry powder: soft pitch=100:40 adds fusing soft pitch, after kneading 1h, compression molding is carried out in taking-up, obtains presoma.
Step 3, by block for step 2 gained presoma, carry out graphitization, graphitization temperature 3000 DEG C, time 14d, obtains semi-finished product.
Step 4, step 3 gained semi-finished product are carried out Mechanical Crushing successively, screening, obtains D
50for the composite graphite finished product of 12-13 μm.
Gained physical and chemical indexes is in table 1, and high rate performance is shown in Fig. 1
Performance test
Respectively the composite graphite prepared in above-described embodiment 1-6 and comparative example 1-2 is adopted the surface topography, granular size etc. of Hitachi, Ltd S4800 sem observation sample; Adopt X-ray diffractometer X ' PertPro, the graphitization of PANalytical test material and anisotropic degree; Adopt the full-automatic specific area of Tristar3000 of Micromeritics Instrument Corp. U.S.A and the specific area of lacunarity analysis instrument test material.Adopt the average grain diameter of Malvern laser particle analyzer MS2000 test material particle size range and feed particles.Adopt the tap density of QuantachromeAutoTap tap density meter test material.
The electrochemical property test of material
Respectively by the composite graphite prepared in above-described embodiment 1-6 and comparative example 1-2, CMC (solid content is 1.2%), binding agent SBR (solid content is 50%) 96.5:1.5:2 mixed pulp in mass ratio, then to be evenly coated on 11 μm of thick Copper Foils and to dry, making surface density 70g/m
2, compacting 1.75g/cm
3pole piece after to be washed into diameter be the circular pole piece of 16mm, in vacuum drying chamber, 120 DEG C of dryings 10 hours are for subsequent use.
With the pole piece of above-mentioned preparation for work electrode, lithium sheet is to electrode, and electrolyte adopts the LiPF of 1mol/L
6eC/DMC/EMC (volume ratio is 1:1:1), two electrode electrolytic pools are assembled in German Braun glove box, carry out constant current charge-discharge with 0.1C current density, voltage range is 0.001V-2.5V, records de-first lithium capacity and the coulombic efficiency first of material.
With the pole piece of above-mentioned preparation for work electrode, lithium cobaltate cathode sheet is to electrode, and electrolyte adopts the LiPF of 1mol/L
6eC/DMC/EMC (volume ratio is 1:1:1), assemble in German Braun glove box electrode displacement measure battery.Above-mentioned battery carries out constant current charge-discharge with 0.1C current density, voltage range is 0.001V-2.5V, and second week starts to carry out constant current charge-discharge circulation with 0.5C current density, after circulating 20 weeks, measure the direct reading of battery by electrode displacement, calculate the expansion rate before and after pole piece circulation.
Materialization test result prepared by embodiment 1-6 and comparative example 1-2 is as shown in table 1.
Table 1
As can be seen from the test result of table 1, composite graphite prepared by embodiment 1-6 combination property in compacting, de-lithium specific capacity, multiplying power, pole piece expansion rate is obviously better than comparative example 1-2.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for composite graphite, is characterized in that, comprises the steps:
S1, provide ultra-fine carbon dust; Described ultra-fine carbon dust comprises green coke and/or carbonaceous mesophase spherules green-ball;
S2, ultra-fine carbon dust to be mixed with binding agent, obtain mixture A, mixture A and catalyst mix, obtain mixture B, then Combined Processing is carried out to mixture B, obtain presoma;
S3, graphitization processing is carried out to presoma, obtain semi-finished product;
S4, semi-finished product are pulverized, spheroidization, coated, screening, obtain described composite graphite.
2. preparation method according to claim 1, is characterized in that, in described step S1, and the D of ultra-fine carbon dust
50for 2-10 μm; The fugitive constituent of described green coke is 5-40%.
3. preparation method according to claim 1 and 2, is characterized in that, described ultra-fine carbon dust comprise in needle coke, pitch coke, same sex Jiao, native graphite, Delanium, carbonaceous mesophase spherules green-ball one or more;
Described needle coke is Raw needle coke and/or ripe Jiao of needle coke; Described pitch coke is pitch coke green coke and/or ripe Jiao of pitch coke; Described same sex Jiao is the burnt green coke of the same sex and/or burnt ripe Jiao of the same sex;
Described needle coke ash content is less than 0.5%; The burnt degree of crystallinity of the described same sex is less than 30%.
4. preparation method according to claim 3, is characterized in that, in mass ratio, native graphite content is below 70wt%, and needle coke content is below 70wt%, and the burnt content of the same sex is below 30wt%, and carbonaceous mesophase spherules green-ball content is below 70wt%.
5. preparation method according to claim 4, is characterized in that, in described ultra-fine carbon dust, native graphite and Raw needle coke weight sum are 70-90wt%, and the burnt green coke content of the same sex is 10-30wt%;
Or carbonaceous mesophase spherules green-ball and native graphite weight sum are greater than 50wt%, the burnt green coke content of the same sex is less than 20wt%, and burnt ripe Jiao of the same sex and/or needle coke content are less than 30wt%.
6., according to the preparation method in claim 1,2,4,5 described in any one, it is characterized in that, in described step S2, described binding agent be selected from middle soft pitch, phenolic resins, epoxy resin, mylar or polyamide one or more;
The softening point of described middle soft pitch is 50-100 DEG C;
Described catalyst be selected from silicon, silicon compound, iron, iron compound, boron, boron compound one or more;
In described mixture B, the ratio that binder content accounts for ultra-fine carbon dust is less than 20wt%; The ratio that catalyst content accounts for ultra-fine carbon dust is less than 30wt%.
7. according to the preparation method in claim 1,2,4,5 described in any one, it is characterized in that, in described step S2, described Combined Processing is selected from solid phase kneading, liquid phase kneading, roll in sheet, fusion, spraying dry, mold pressing, isostatic pressed, carbonization one or more; Described liquid phase kneading temperature is 100-300 DEG C, and the liquid phase kneading time is 1-2h;
In described step S3, the temperature of described graphitization processing is 2700-3200 DEG C;
In described step S4, described coated process is selected from the one in the coated or mechanical fusion of liquid phase coating, solid phase; The clad material that described coated process adopts be selected from pitch, resin, electrically conductive graphite one or more;
Described screen size D
50for 4-30 μm.
8. preparation method according to claim 7, is characterized in that, described coated process is liquid phase coating, after described liquid phase coating, also comprise carbonization treatment before screening process; The temperature of described carbonization treatment is 600-1500 DEG C.
9. a composite graphite, is characterized in that, described composite graphite is prepared by the method in claim 1-8 described in any one.
10. a lithium ion battery, is characterized in that, comprises positive pole stacked successively, barrier film and negative pole; Described negative pole comprises negative current collector and is positioned at the negative material on described negative current collector, and described negative material comprises composite graphite according to claim 9.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510621926.7A CN105098184A (en) | 2015-09-25 | 2015-09-25 | Preparation method of composite graphite, composite graphite and lithium ion battery |
| PCT/CN2016/099767 WO2017050260A1 (en) | 2015-09-25 | 2016-09-22 | Method for preparing composite graphite, composite graphite and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510621926.7A CN105098184A (en) | 2015-09-25 | 2015-09-25 | Preparation method of composite graphite, composite graphite and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105098184A true CN105098184A (en) | 2015-11-25 |
Family
ID=54578155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510621926.7A Pending CN105098184A (en) | 2015-09-25 | 2015-09-25 | Preparation method of composite graphite, composite graphite and lithium ion battery |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN105098184A (en) |
| WO (1) | WO2017050260A1 (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789627A (en) * | 2016-03-22 | 2016-07-20 | 福建翔丰华新能源材料有限公司 | Preparation method of high-performance graphite negative electrode material for lithium ion battery |
| WO2017050260A1 (en) * | 2015-09-25 | 2017-03-30 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing composite graphite, composite graphite and lithium ion battery |
| CN106654269A (en) * | 2017-01-06 | 2017-05-10 | 江西紫宸科技有限公司 | Graphite negative electrode material used for power lithium ion battery and preparation method and application of graphite negative electrode material |
| CN107293697A (en) * | 2017-07-26 | 2017-10-24 | 大连宏光锂业股份有限公司 | A kind of power-type lithium ion battery negative material production method |
| CN107579252A (en) * | 2017-09-07 | 2018-01-12 | 福建杉杉科技有限公司 | A kind of high power charcoal bag covers the preparation method of artificial plumbago negative pole material |
| CN107706387A (en) * | 2017-10-09 | 2018-02-16 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of composite negative pole material, its preparation method and lithium ion battery |
| CN108467268A (en) * | 2018-04-28 | 2018-08-31 | 深圳市赛普戴蒙德科技有限公司 | A kind of modified form graphite sheet and its manufacturing method |
| CN108640682A (en) * | 2018-04-28 | 2018-10-12 | 深圳市赛普戴蒙德科技有限公司 | A kind of graphite sheet and its manufacturing method |
| CN108658596A (en) * | 2018-04-28 | 2018-10-16 | 深圳市赛普戴蒙德科技有限公司 | graphite sheet and its manufacturing method |
| CN108933240A (en) * | 2018-06-26 | 2018-12-04 | 石家庄尚太科技有限公司 | A kind of preparation method and negative electrode material of high-density lithium ion battery negative electrode material |
| CN109911892A (en) * | 2017-12-13 | 2019-06-21 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of the powerful composite graphite negative electrode material of high capacity |
| CN109950495A (en) * | 2019-03-27 | 2019-06-28 | 溧阳紫宸新材料科技有限公司 | Preparation method, negative electrode material and the lithium ion battery of high magnification graphite cathode material |
| CN111232969A (en) * | 2018-11-28 | 2020-06-05 | 上海杉杉科技有限公司 | Composite intermediate phase negative electrode material, lithium ion secondary battery, preparation method and application |
| CN114156471A (en) * | 2020-09-07 | 2022-03-08 | 湖南中科星城石墨有限公司 | Graphite negative electrode material and preparation method and application thereof |
| CN114203979A (en) * | 2020-09-17 | 2022-03-18 | 湖南中科星城石墨有限公司 | Graphite negative electrode material and preparation method and application thereof |
| CN114477161A (en) * | 2021-12-29 | 2022-05-13 | 惠州锂威新能源科技有限公司 | Graphite material, preparation method thereof, negative plate and secondary battery |
| CN114804093A (en) * | 2022-05-30 | 2022-07-29 | 乌海宝杰新能源材料有限公司 | Novel black phosphorus graphite composite negative electrode material and preparation method thereof |
| CN114804091A (en) * | 2022-04-26 | 2022-07-29 | 李鑫 | Molten iron-assisted graphitized artificial graphite negative electrode material and manufacturing method thereof |
| CN114927685A (en) * | 2022-06-28 | 2022-08-19 | 山西沁新能源集团股份有限公司 | Catalytic graphitization coal-based negative electrode material and preparation method thereof |
| CN115872744A (en) * | 2022-12-14 | 2023-03-31 | 湖南大学 | Method for preparing high-performance binder-free carbon graphite material by solid-phase densification |
| WO2023082515A1 (en) * | 2021-11-09 | 2023-05-19 | 微宏动力系统（湖州）有限公司 | Negative electrode material and preparation method therefor |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111232968A (en) * | 2018-11-28 | 2020-06-05 | 上海杉杉科技有限公司 | Composite graphite negative electrode material, lithium ion secondary battery, preparation method and application |
| CN114162814B (en) * | 2020-08-20 | 2024-05-10 | 洛阳月星新能源科技有限公司 | Modification method of graphite |
| CN114583119B (en) * | 2020-12-01 | 2024-02-27 | 湖南中科星城石墨有限公司 | Preparation method of composite particles, composite particles prepared by using preparation method and application of composite particles |
| CN112938960B (en) * | 2021-01-29 | 2023-09-29 | 乌海宝杰新能源材料有限公司 | Preparation method of high-compaction-density and low-specific-surface-area negative electrode material |
| CN113097479B (en) * | 2021-03-30 | 2023-04-07 | 吴耀帮 | Preparation method of quick-charging type lithium ion battery negative electrode powder and application of quick-charging type lithium ion battery negative electrode powder in lithium ion battery |
| CN113526500B (en) * | 2021-07-20 | 2023-05-26 | 安徽科达新材料有限公司 | Preparation method of high-performance artificial graphite anode material |
| CN113816370B (en) * | 2021-11-23 | 2022-02-08 | 山西沁新能源集团股份有限公司 | Coal-based graphite composite material, preparation method thereof and battery using same |
| CN114702316B (en) * | 2022-03-23 | 2023-05-30 | 湖南大学 | Preparation method and application of low-cost high-purity graphite material |
| CN114824162A (en) * | 2022-04-12 | 2022-07-29 | 湖南阿斯米科技有限公司 | Graphitization process and system for graphite negative electrode material of lithium ion battery |
| CN114824233A (en) * | 2022-05-31 | 2022-07-29 | 深圳市翔丰华科技股份有限公司 | Preparation method of high-energy-density quick-charging graphite negative electrode material of lithium battery |
| CN115448305B (en) * | 2022-09-19 | 2023-11-17 | 惠州锂威新能源科技有限公司 | Graphite matrix and preparation method thereof, and quick-charge graphite and preparation method thereof |
| CN116496087B (en) * | 2023-05-22 | 2024-05-24 | 湖南大学 | Superfine structure special carbon material and preparation method thereof |
| CN117199363B (en) * | 2023-08-29 | 2024-06-21 | 深圳市贝特瑞新能源技术研究院有限公司 | Graphite negative electrode material, preparation method thereof and battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811758A (en) * | 2014-02-19 | 2014-05-21 | 新乡市赛日新能源科技有限公司 | Preparation method for synthesizing graphite particle negative electrode material |
| CN104143635A (en) * | 2013-05-10 | 2014-11-12 | 宁波杉杉新材料科技有限公司 | Synthetic graphite negative electrode material and preparation method thereof |
| CN104218214A (en) * | 2013-05-28 | 2014-12-17 | 上海杉杉新能源科技有限公司 | Lithium ion battery negative electrode material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102951633A (en) * | 2012-11-21 | 2013-03-06 | 芜湖浙鑫新能源有限公司 | Graphite spheroidization method and production system thereby |
| CN103855369A (en) * | 2012-12-05 | 2014-06-11 | 上海杉杉科技有限公司 | Lithium battery negative electrode material and preparation method thereof |
| CN104143641B (en) * | 2013-05-10 | 2018-07-31 | 福建杉杉科技有限公司 | A kind of interphase negative material and preparation method thereof |
| CN104425823B (en) * | 2013-09-11 | 2019-04-19 | 宁波杉杉新材料科技有限公司 | A kind of artificial graphite cathode material for lithium ion batteries and preparation method thereof |
| CN105098184A (en) * | 2015-09-25 | 2015-11-25 | 深圳市贝特瑞新能源材料股份有限公司 | Preparation method of composite graphite, composite graphite and lithium ion battery |
-
2015
- 2015-09-25 CN CN201510621926.7A patent/CN105098184A/en active Pending
-
2016
- 2016-09-22 WO PCT/CN2016/099767 patent/WO2017050260A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104143635A (en) * | 2013-05-10 | 2014-11-12 | 宁波杉杉新材料科技有限公司 | Synthetic graphite negative electrode material and preparation method thereof |
| CN104218214A (en) * | 2013-05-28 | 2014-12-17 | 上海杉杉新能源科技有限公司 | Lithium ion battery negative electrode material and preparation method thereof |
| CN103811758A (en) * | 2014-02-19 | 2014-05-21 | 新乡市赛日新能源科技有限公司 | Preparation method for synthesizing graphite particle negative electrode material |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017050260A1 (en) * | 2015-09-25 | 2017-03-30 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing composite graphite, composite graphite and lithium ion battery |
| CN105789627A (en) * | 2016-03-22 | 2016-07-20 | 福建翔丰华新能源材料有限公司 | Preparation method of high-performance graphite negative electrode material for lithium ion battery |
| CN106654269A (en) * | 2017-01-06 | 2017-05-10 | 江西紫宸科技有限公司 | Graphite negative electrode material used for power lithium ion battery and preparation method and application of graphite negative electrode material |
| CN106654269B (en) * | 2017-01-06 | 2019-03-22 | 溧阳紫宸新材料科技有限公司 | Graphite cathode material and its preparation method and application for power lithium-ion battery |
| CN107293697A (en) * | 2017-07-26 | 2017-10-24 | 大连宏光锂业股份有限公司 | A kind of power-type lithium ion battery negative material production method |
| CN107293697B (en) * | 2017-07-26 | 2019-07-12 | 大连宏光锂业股份有限公司 | A kind of power-type lithium ion battery negative electrode material production method |
| CN107579252A (en) * | 2017-09-07 | 2018-01-12 | 福建杉杉科技有限公司 | A kind of high power charcoal bag covers the preparation method of artificial plumbago negative pole material |
| CN107706387A (en) * | 2017-10-09 | 2018-02-16 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of composite negative pole material, its preparation method and lithium ion battery |
| CN107706387B (en) * | 2017-10-09 | 2021-11-05 | 贝特瑞新材料集团股份有限公司 | Composite negative electrode material, preparation method thereof and lithium ion battery |
| CN109911892A (en) * | 2017-12-13 | 2019-06-21 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of the powerful composite graphite negative electrode material of high capacity |
| CN109911892B (en) * | 2017-12-13 | 2021-12-31 | 宁波杉杉新材料科技有限公司 | Preparation method of composite graphite negative electrode material with high capacity and high multiplying power |
| CN108658596B (en) * | 2018-04-28 | 2021-04-23 | 深圳市赛普戴蒙德科技有限公司 | Graphite plate and manufacturing method thereof |
| CN108467268B (en) * | 2018-04-28 | 2021-11-26 | 深圳市赛普戴蒙德科技有限公司 | Improved graphite plate and manufacturing method thereof |
| CN108467268A (en) * | 2018-04-28 | 2018-08-31 | 深圳市赛普戴蒙德科技有限公司 | A kind of modified form graphite sheet and its manufacturing method |
| CN108640682A (en) * | 2018-04-28 | 2018-10-12 | 深圳市赛普戴蒙德科技有限公司 | A kind of graphite sheet and its manufacturing method |
| CN108640682B (en) * | 2018-04-28 | 2021-04-23 | 深圳市赛普戴蒙德科技有限公司 | Graphite plate and manufacturing method thereof |
| CN108658596A (en) * | 2018-04-28 | 2018-10-16 | 深圳市赛普戴蒙德科技有限公司 | graphite sheet and its manufacturing method |
| CN108933240A (en) * | 2018-06-26 | 2018-12-04 | 石家庄尚太科技有限公司 | A kind of preparation method and negative electrode material of high-density lithium ion battery negative electrode material |
| CN111232969A (en) * | 2018-11-28 | 2020-06-05 | 上海杉杉科技有限公司 | Composite intermediate phase negative electrode material, lithium ion secondary battery, preparation method and application |
| CN109950495A (en) * | 2019-03-27 | 2019-06-28 | 溧阳紫宸新材料科技有限公司 | Preparation method, negative electrode material and the lithium ion battery of high magnification graphite cathode material |
| CN109950495B (en) * | 2019-03-27 | 2022-06-14 | 溧阳紫宸新材料科技有限公司 | Preparation method of high-rate graphite negative electrode material, negative electrode material and lithium ion battery |
| CN114156471A (en) * | 2020-09-07 | 2022-03-08 | 湖南中科星城石墨有限公司 | Graphite negative electrode material and preparation method and application thereof |
| CN114203979A (en) * | 2020-09-17 | 2022-03-18 | 湖南中科星城石墨有限公司 | Graphite negative electrode material and preparation method and application thereof |
| CN114203979B (en) * | 2020-09-17 | 2024-05-17 | 湖南中科星城石墨有限公司 | Graphite negative electrode material and preparation method and application thereof |
| WO2023082515A1 (en) * | 2021-11-09 | 2023-05-19 | 微宏动力系统（湖州）有限公司 | Negative electrode material and preparation method therefor |
| CN114477161A (en) * | 2021-12-29 | 2022-05-13 | 惠州锂威新能源科技有限公司 | Graphite material, preparation method thereof, negative plate and secondary battery |
| CN114804091A (en) * | 2022-04-26 | 2022-07-29 | 李鑫 | Molten iron-assisted graphitized artificial graphite negative electrode material and manufacturing method thereof |
| CN114804091B (en) * | 2022-04-26 | 2023-09-22 | 深圳市钢昱碳晶科技有限公司 | Molten iron-assisted graphitized artificial graphite negative electrode material and manufacturing method thereof |
| CN114804093A (en) * | 2022-05-30 | 2022-07-29 | 乌海宝杰新能源材料有限公司 | Novel black phosphorus graphite composite negative electrode material and preparation method thereof |
| CN114927685A (en) * | 2022-06-28 | 2022-08-19 | 山西沁新能源集团股份有限公司 | Catalytic graphitization coal-based negative electrode material and preparation method thereof |
| CN115872744A (en) * | 2022-12-14 | 2023-03-31 | 湖南大学 | Method for preparing high-performance binder-free carbon graphite material by solid-phase densification |
| CN115872744B (en) * | 2022-12-14 | 2023-08-08 | 湖南大学 | Method for preparing high-performance binder-free carbon graphite material by solid-phase densification |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017050260A1 (en) | 2017-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105098184A (en) | Preparation method of composite graphite, composite graphite and lithium ion battery | |
| CN107785560B (en) | High-performance silicon-carbon negative electrode material and preparation method thereof | |
| CN102593434B (en) | Composite graphite particles for lithium secondary battery and preparation method thereof | |
| CN104085883B (en) | A kind of man-made graphite cathode material for lithium ion battery and preparation method thereof | |
| CN109830669B (en) | Preparation method of high-rate artificial graphite negative electrode material | |
| CN106654235B (en) | Composite graphite material, preparation method thereof and lithium ion battery containing composite graphite material | |
| CN106981657B (en) | A kind of graphite cathode material and preparation method thereof | |
| CN103518279B (en) | Non-aqueous secondary battery material with carbon element, the negative pole using this material with carbon element and non-aqueous secondary battery | |
| CN100579899C (en) | Method of producing lithium iron phosphate with high compacted density and excellent adhesive property | |
| CN103647056B (en) | SiOx based composite negative electrode material, preparation method and battery | |
| US8728668B2 (en) | Negative electrode active material for lithium ion rechargeable battery and negative electrode using the same | |
| CN103811717B (en) | Lithium ion battery cathode material of nucleocapsid structure and preparation method thereof | |
| CN108550850A (en) | A kind of high power capacity high-pressure solid artificial plumbago negative pole material and preparation method thereof, lithium ion battery | |
| CN103811758B (en) | A kind of preparation method of synthetic graphite particle negative material | |
| CN108054357A (en) | Power lithium-ion battery coal base composite negative pole material and preparation method thereof | |
| CN104143641B (en) | A kind of interphase negative material and preparation method thereof | |
| CN103311520B (en) | A kind of lithium ion battery composite graphite negative electrode material and preparation method thereof | |
| CN105977458A (en) | Nano diamond powder and graphene composite electrode material and preparation method thereof | |
| CN101908627B (en) | Cathode material of lithium ion secondary battery and preparation method thereof | |
| CN103855369A (en) | Lithium battery negative electrode material and preparation method thereof | |
| CN103794765A (en) | Lithium ion battery graphite negative electrode material and preparation method thereof | |
| CN103078090A (en) | Lithium ion power battery composite cathode material and its preparation method | |
| CN107507979A (en) | A kind of preparation method of high jolt ramming artificial plumbago negative pole material | |
| CN105789627A (en) | Preparation method of high-performance graphite negative electrode material for lithium ion battery | |
| CN105244485A (en) | High capacity and high magnification composite graphite material for lithium ion battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151125 |
|
| RJ01 | Rejection of invention patent application after publication |