CN107785560A - A kind of high performance silicon carbon negative pole material and preparation method thereof - Google Patents

A kind of high performance silicon carbon negative pole material and preparation method thereof Download PDF

Info

Publication number
CN107785560A
CN107785560A CN201711128166.1A CN201711128166A CN107785560A CN 107785560 A CN107785560 A CN 107785560A CN 201711128166 A CN201711128166 A CN 201711128166A CN 107785560 A CN107785560 A CN 107785560A
Authority
CN
China
Prior art keywords
silicon
nano
graphite
pitch
preparation
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.)
Granted
Application number
CN201711128166.1A
Other languages
Chinese (zh)
Other versions
CN107785560B (en
Inventor
李进
杨娟玉
卢世刚
曹宗双
赵春荣
于冰
史碧梦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Automotive Battery Research Institute Co Ltd
Original Assignee
China Automotive Battery Research Institute Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Automotive Battery Research Institute Co Ltd filed Critical China Automotive Battery Research Institute Co Ltd
Priority to CN201711128166.1A priority Critical patent/CN107785560B/en
Publication of CN107785560A publication Critical patent/CN107785560A/en
Application granted granted Critical
Publication of CN107785560B publication Critical patent/CN107785560B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A kind of high performance silicon carbon negative pole material and preparation method thereof, the preparation method comprises the following steps：(1) silicon is disperseed to obtain nano-silicon dispersion liquid by liquid phase ball milling in a solvent, then adds graphite and realize that nano-silicon mixes with the uniform of graphite by liquid phase ball milling；(2) step (1) is mixed into gained slurry granulation and realizes that graphite/nano-silicon Composite is granulated；(3) step (2) products therefrom and pitch are realized that the Composite of graphite/nano-silicon/pitch is granulated using the broken method of kneading compacting, after being handled again through mechanical fusion, a step is realized the spheroidization of graphite/nano-silicon/pitch composite particles and uniformly coated；(4) after being carbonized, break up, sieve, the high performance silicon carbon compound cathode materials are obtained.The preparation method of the present invention is simple, low cost, is easy to large-scale production high performance silicon carbon negative pole material.

Description

A kind of high performance silicon carbon negative pole material and preparation method thereof
Technical field
The invention belongs to cell negative electrode material technical field, and in particular to a kind of high performance silicon carbon negative pole material and its preparation Method.
Background technology
Operating voltage is high, have extended cycle life, memory-less effect, self discharge effect is small, environment is friendly because it has for lithium ion battery The advantages that good, it has been widely used in mobile electronic device, scale energy-accumulating power station and electric automobile.Currently, it is commercialized Lithium ion battery negative material mainly use graphite negative electrodes material, but its theoretical specific capacity is only 372mAh/g, Wu Faman Foot future more high-energy-density and the requirement of high power density lithium ion battery development.Therefore, the height ratio capacity for finding replacement carbon is born Pole material turns into an important developing direction.
Due to being considered as with highest lithium storage content (theoretical specific capacity 4200mAh/g) and abundant resource, silicon materials It is most potential to be expected to turn into lithium ion battery negative material of future generation.However, because larger volume during Li insertion extraction becomes Change the silicon material structure destruction and material efflorescence brought, electrode structure can be caused to destroy, cause silicon active component to lose electrical contact. In addition the efflorescence of material and huge Volume Changes, can cause being continuously generated for SEI films, so as to cause the electrochemistry of battery to circulate Less stable, hinder scale application of the silicon materials as lithium ion battery negative material.
To solve the problems, such as that silicium cathode material exists in the application, researchers mainly pass through the nanosizing means of silicon at present To reduce the expansion of the absolute volume of silicon, material efflorescence is avoided.But simple nanosizing can not solve nano-silicon in cyclic process " electrochemistry sintering " and aggravation side reaction caused by SEI films the problem of being continuously generated.Therefore, it is necessary to using nanosizing and again The means that combination is combined, it is existing each in actual applications to solve silicon by constructing the method for multi-component multi-layer time composite Kind problem.The most of silicon-carbon cathode material reported at present is mostly the core shell structure of Surface coating processing, and kernel is loose more The structure in hole, loose structure maintain the pattern of kernel by providing the silicon space that expansion needs.But this inside configuration hole Gap rate is excessive, although being advantageous to improve the cyclical stability of material, material is not pressure-resistant, clad low intensity, material vibration density Bulk density that is low, and then reducing battery is spent, and under the conditions of same surface density, pole piece is blocked up and can cause the bad of battery performance Change.
Therefore, to meet the needs of high specific energy lithium ion battery of new generation development, it is necessary to while improve silicon-carbon cathode material Capacity, the surface density of tap density and pole piece.
As CN103682287A discloses a kind of lithium ion battery silicon substrate for the high compacted density for embedding compound nucleocapsid structure Composite negative pole material.The invention is combined using mechanical lapping, mechanical fusion, isotropism pressurized treatments with carbon coating technology Mode realizes the preparation of Si-C composite material.But mechanical lapping is refer in this method and prepares the process of hollow graphite excessively Ideal, real process easily cause that graphite is broken rather than village hollowing；Mechanofusion process also mainly realizes nano-silicon in graphite Surface disperses, and the later stage will also carry out carbon coating processing；Hold very much in addition, carrying out break process again after same sex pressurization and high temperature cabonization The destruction of surface coating layer is easily caused, is unable to reach preferable core shell structure.CN103647056A discloses a kind of SiOXBase is answered Negative material and preparation method thereof is closed, nano-carbon material is realized in particle SiO using the method for mechanical fusion in the inventionXTable Face disperses, and the later stage needs also exist for further carrying out carbon coating processing.
The content of the invention
Therefore, an object of the present invention is to provide a kind of preparation method of high performance silicon carbon negative pole material, the preparation Negative material made from method has high tap density, solves silicon-carbon cathode material under the conditions of higher surface density, pole The problem of piece is thicker, chemical property is poor.And the preparation method of the present invention is simple, low cost, is easy to the high property of large-scale production Can silicon-carbon cathode material.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of high performance silicon carbon negative pole material, comprises the following steps：
(1) silicon is disperseed to obtain nano-silicon dispersion liquid by liquid phase ball milling in a solvent, then adds graphite and pass through liquid phase Ball milling realizes that nano-silicon mixes with the uniform of graphite；
(2) step (1) is mixed into gained slurry granulation and realizes that graphite/nano-silicon Composite is granulated, while ensure nano-silicon In the dispersed of graphite surface；
(3) kneading-compacting-broken method is used to realize graphite/nano-silicon/drip step (2) products therefrom and pitch Blue or green Composite is granulated, then after being handled through mechanical fusion, a step realizes the spheroidization of graphite/nano-silicon/pitch composite particles With uniform cladding；
(4) after being carbonized, break up, sieve, the high performance silicon carbon compound cathode materials are obtained.
Compared with prior art, the present invention is answered graphite/nano-silicon/pitch plasticity using mechanofusion process under high rotating speed The shaping operation of particle is closed, to improve the sphericity of material and tap density, wherein pitch is to be formed after melt kneading-compacting Continuous phase, and non-particulate.Fine and close, uniform, the complete cladding of pitch is realized in this process, reduces the ratio table of material Area, preferable nucleocapsid structure silicon-carbon composite cathode material is successfully prepared, while by mechanofusion process, realizes carbon Clad is combined closely with graphite/nano-silicon kernel, adds bond strength, and stabilization is provided for electronics and lithium ion transport Effective transmission channel.
Preferably, silicone content is not less than 99% in raw materials used silicon in step (1).
Preferably, raw materials used silicon is the silica flour of micron silica flour, preferably 1-5 μm of median particle diameter, in being more preferably It is worth the silica flour of 3 μm of particle diameter.
Preferably, solvent is combination one kind or two or more in ethanol, methanol, isopropanol, n-butanol, acetone, toluene etc..
Preferably, the mass ratio of raw materials used silicon and solvent is 1:5-15, preferably 1:9.
Preferably, ball-milling medium is zirconia ball, preferably diameter 0.1-0.5mm zirconia ball, more preferably Diameter 0.3mm zirconia ball.
Preferably, the ball material mass ratio of ball milling is 5-15 when preparing nano-silicon dispersion liquid:1, preferably 10:1.
Preferably, the rotating speed of ball milling is 1500-2000rpm, preferably 1800rpm when preparing nano-silicon dispersion liquid, ball milling Time be more than 5 hours, preferably 10 hours.
Preferably, the mass ratio of graphite and raw materials used silicon is 1-3:1, preferably 1.7:1.
Preferably, the rotating speed of ball milling is 500-1500rpm, preferably 1000rpm after adding graphite, and the time of ball milling is More than 0.5 hour, preferably 1 hour.The rotating speed of ball milling is preferably shorter than ball milling when preparing nano-silicon dispersion liquid after addition graphite Rotating speed.
Preferably, the ratio of grinding media to material of ball milling is controlled 3 after addition graphite:1-15:1 is advisable.
Ultra-fine ball mill can be used to carry out for ball milling.
Preferably, the method using spray drying is granulated in step (2).
Preferably, the Composite granulation process of graphite/nano-silicon/pitch is in step (3)：Step (2) products therefrom With hot-rolling pressure after the hot kneading of pitch, powder body material is broken into after cooling；Powder body material isostatic pressing is obtained into graphite/nanometer again Silicon/pitch bulk green compact；Then by the broken sieving of green compact.
Preferably, pitch is the coal asphalt or petroleum asphalt of more than 60 DEG C of softening temperature.
Preferably, the mass ratio of step (2) products therefrom and pitch is 1-4:1, preferably 2:1.
Preferably, the temperature of hot kneading is 100-300 DEG C, and preferably 120-250 DEG C, the time is more than 1h, preferably 2h.
Preferably, the temperature of hot-rolling pressure is 100-300 DEG C, preferably 120-250 DEG C.The temperature of hot-rolling pressure and hot kneading Temperature may be the same or different, preferably identical.Can hot-rolling be pressed into about 2mm thickness rubber dress.
Material can be put into rubber package set and be carried out on isostatic pressing machine by isostatic pressing.
Preferably, pressure during isostatic pressing is 150-300MPa, preferably 200MPa, and the time of isostatic pressing is More than 5min, preferably 10min.
Material controlled porosity is realized by the control of kneading and pressing process parameter.
Preferably, linear velocity during mechanical fusion is 10-50m/s, and the time of mechanical fusion is 3-60min, preferably 15- 30min.Mechanical fusion can be carried out in mechanical fusion machine.
With the raising of mechanical fusion line speed, the increase of time of fusion, sphericity and the tap density increase of material.Selection Linear velocity during mechanical fusion is 10-50m/s, and the time of mechanical fusion may be such that sphericity and the jolt ramming of material for 3-60min Density is optimal.
The carbon coating layer densification of graphite/nano-silicon/pitch composite particles is made in said process of the present invention and intensity is high, uniformly Property is good, and the thickness control of carbon coating layer is at 0.05-2 μm, by the change of pitch addition, realizes that coating thickness is controllable.
In a preferred embodiment, the process of step (3) is：Take powdery intermediate product obtained by the above-mentioned spray drying of 2kg With 1kg modified coal tar pitches, the hot kneading 2h at a temperature of 160-180 DEG C；By kneading product at 160-180 DEG C hot roller process, into The rubber dress of about 2mm thickness, powder body material is broken into after cooling；Powder body material is put into rubber package set again, in isostatic pressing machine Isostatic pressing 10 minutes under middle 200MPa pressure, obtain graphite/nano-silicon/pitch bulk green compact；Then will be into graphite/nanometer After the broken sieving of silicon/pitch green compact, the mechanical fusion 20min under 45m/s linear velocity is put into mechanical fusion machine, obtains stone Ink/nano-silicon/pitch composite particles.
Preferably, carbonization is carried out under inert atmosphere protection in step (4), the temperature of carbonization is 800-1000 DEG C, excellent Elect 900 DEG C as, the time of carbonization is more than 2h, preferably 4h.
Silicone content is 20-40% in silicon-carbon composite cathode material.
An object of the present invention, which also resides in, provides high performance silicon carbon negative pole material prepared by a kind of the method for the invention.
The preparation method of the present invention uses mechanical fusion technique, has using the compound precursor particle of graphite/nano-silicon/pitch There is the characteristics of certain plasticity, graphite/compound precursor of nano-silicon/pitch is realized by the step of effect one of shearing force and extruding force The spheroidization of grain and the complete cladding of pitch；Substantially increase the tap density of material, surface forms one layer of densification and uniform Clad.
By mechanofusion process, combining closely for carbon coating layer and graphite/nano-silicon kernel is realized, adds combination Intensity, provide for electronics and lithium ion transport and stablize effective transmission channel.Pitch inside particle cracks to form three dimensional network Network conductive structure, and there is preferable intensity, improve the inner conductive of material and the structural stability of particle.
Nano-silicon is dispersed among graphite surface or graphite flake layer hole, and is dripped by the three-dimensional with some strength Green grass or young crops cracks carbon to keep the stability of inner core and conductive network, reaches good cyclical stability and high rate performance.
Si-C composite material prepared by the preparation method of the present invention, there is high power capacity, good cycling stability；Material vibration density Degree is high, and processing characteristics is excellent；Fine and close carbon coating layer is formed, reduces material specific surface area, is advantageous to suppress electrolyte degraded Side reaction occur, improve the coulombic efficiency of Si-C composite material；The method of the present invention is compared with traditional handicraft, the production of material Rate is higher, can reach more than 95%.
Brief description of the drawings
Fig. 1 is the process chart of preparation method of the present invention；
Fig. 2 is the SEM figures of the Si-C composite material prepared in embodiment 1；
Fig. 3 is the section SEM for the preparing Si-C composite material figures in embodiment 1；
Fig. 4 is the size distribution curve of the Si-C composite material prepared in embodiment 1；
Fig. 5 is the constant current charge-discharge curve of the Si-C composite material prepared in embodiment 1；
Fig. 6 is the stable circulation linearity curve of the Si-C composite material prepared in embodiment 1；
Fig. 7 is the G/Si@C Si-C composite materials SEM figures without mechanical fusion processing in comparative example 1.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
Fig. 1 is the process chart of preparation method of the present invention.
Embodiment 1：
To take 2kg median particle diameters be 3 μm, silicone content is the micron silica flour more than 99%, is added in 18kg alcohol solvents, is surpassed After sound disperses 30min, pour into ultra-fine ball mill cavity.A diameter of 0.3mm zirconia ball is used as ball-milling medium, ratio of grinding media to material (mass ratio) is 10:1, ball milling 10 hours under 1800rpm rotating speed, obtain nano-silicon dispersion liquid.Into nano-silicon dispersion liquid 3.4kg flake graphites are added, uniform mixed slurry is obtained after ball milling is scattered 1 hour under 1000rpm rotating speeds.Mixed slurry is entered Row spray drying, obtains graininess composite granule.
Powdery intermediate product and 1kg modified coal tar pitches obtained by the above-mentioned spray drying of 2kg are taken, heat is mixed at a temperature of 160-180 DEG C Pinch 2h；By kneading product, hot roller process, the rubber into about 2mm thickness are filled at 160-180 DEG C, and powder material is broken into after cooling Material；Powder body material is put into rubber package set again, isostatic pressing 10 minutes under 200MPa pressure, obtain stone in isostatic pressing machine Ink/nano-silicon/pitch bulk green compact；Then after sieving being crushed into graphite/nano-silicon/pitch green compact, it is put into mechanical fusion machine In under 45m/s linear velocity mechanical fusion 20min, obtain graphite/nano-silicon/pitch composite particles；In inert atmosphere protection Lower 900 DEG C are calcined 4 hours；The silicon-carbon composite cathode material of silicone content 33% is obtained after breaing up and sieving.
Fig. 2 is silicon-carbon composite cathode material SEM (SEM) figure manufactured in the present embodiment, it can be seen that silicon-carbon Composite has a preferable sphericity, and surface is smooth.Fig. 3 is silicon-carbon composite cathode material section SEM manufactured in the present embodiment Figure, it can be seen that nano-silicon is dispersed in the surface of graphite, hole be present between graphite flake layer, is reserved for the volumetric expansion of silicon Space, material surface have coated one layer of fine and close amorphous carbon layer, and thickness is at hundreds of nanometers.Fig. 4 is Si-C composite material grain Degree distribution, the median particle diameter of material is at about 13 μm or so.
Table 1 shows that the performance test results of material are made in the present embodiment.As known from Table 1, material, which has, less compares table Area, reach 2.4m2/ g, material show higher tap density, reach 0.96g/cm3.Fig. 5 and Fig. 6 is respectively that silicon-carbon is compound The first all charging and discharging curves and stable circulation linearity curve of negative material.It can be seen that the first all reversible capacities of Si-C composite material are 857mAh/g, first all coulombic efficiencies 83.7%, 50 weeks circulation volume conservation rates 75.9%.
Fig. 7 is not prepare Si-C composite material SEM figures using mechanical fusion technique in comparative example 1, it can be seen that material Sphericity is poor, imperfect in random graininess, surface coating layer.Material tap density is only 0.63g/ as known from Table 1 cm3, specific surface area 6.7m2/ g, tap density is relatively low, and specific surface area is larger.
Embodiment 2：
To take 2kg median particle diameters be 3 μm, silicone content is the micron silica flour more than 99%, is added in 18kg alcohol solvents, is surpassed After sound disperses 30min, pour into ultra-fine ball mill cavity.A diameter of 0.3mm zirconia ball is used as ball-milling medium, ratio of grinding media to material (mass ratio) is 10:1, ball milling 10 hours under 1800rpm rotating speed, obtain nano-silicon dispersion liquid.Into nano-silicon dispersion liquid 3.4kg flake graphites are added, uniform mixed slurry is obtained after ball milling is scattered 1 hour under 1000rpm rotating speeds.Mixed slurry is entered Row spray drying, obtains graininess composite granule.
Powdery intermediate product and 1kg modified coal asphalts obtained by the above-mentioned spray drying of 2kg are taken, it is hot at a temperature of 120-140 DEG C Kneading 2h；By kneading product, hot roller process, the rubber into about 2mm thickness are filled at 120-140 DEG C, and powder is broken into after cooling Material；Powder body material is put into rubber package set again, isostatic pressing 10 minutes under 200MPa pressure, are obtained in isostatic pressing machine Graphite/nano-silicon/pitch bulk green compact；Then after sieving being crushed into graphite/nano-silicon/pitch green compact, it is put into mechanical fusion In machine under 40m/s linear velocity mechanical fusion 30min, obtain graphite/nano-silicon/pitch composite particles；Protected in inert atmosphere Lower 900 DEG C are protected to calcine 4 hours；The silicon-carbon composite cathode material of silicone content 33% is obtained after breaing up and sieving.
Embodiment 3：
To take 2kg median particle diameters be 3 μm, silicone content is the micron silica flour more than 99%, is added in 18kg alcohol solvents, is surpassed After sound disperses 30min, pour into ultra-fine ball mill cavity.A diameter of 0.3mm zirconia ball is used as ball-milling medium, ratio of grinding media to material (mass ratio) is 10:1, ball milling 10 hours under 1800rpm rotating speed, obtain nano-silicon dispersion liquid.Into nano-silicon dispersion liquid 3.4kg flake graphites are added, uniform mixed slurry is obtained after ball milling is scattered 1 hour under 1000rpm rotating speeds.Mixed slurry is entered Row spray drying, obtains graininess composite granule.
Powdery intermediate product and 1kg modified coal asphalts obtained by the above-mentioned spray drying of 2kg are taken, it is hot at a temperature of 120-140 DEG C Kneading 2h；By kneading product, hot roller process, the rubber into about 2mm thickness are filled at 120-140 DEG C, and powder is broken into after cooling Material；Powder body material is put into rubber package set again, isostatic pressing 10 minutes under 200MPa pressure, are obtained in isostatic pressing machine Graphite/nano-silicon/pitch bulk green compact；Then after sieving being crushed into graphite/nano-silicon/pitch green compact, it is put into mechanical fusion In machine under 35m/s linear velocity mechanical fusion 30min, obtain graphite/nano-silicon/pitch composite particles；Protected in inert atmosphere Lower 900 DEG C are protected to calcine 4 hours；The silicon-carbon composite cathode material of silicone content 33% is obtained after breaing up and sieving.
Embodiment 4：
To take 2kg median particle diameters be 3 μm, silicone content is the micron silica flour more than 99%, is added in 18kg alcohol solvents, is surpassed After sound disperses 30min, pour into ultra-fine ball mill cavity.A diameter of 0.3mm zirconia ball is used as ball-milling medium, ratio of grinding media to material (mass ratio) is 10:1, ball milling 10 hours under 1800rpm rotating speed, obtain nano-silicon dispersion liquid.Into nano-silicon dispersion liquid 3.4kg flake graphites are added, uniform mixed slurry is obtained after ball milling is scattered 1 hour under 1000rpm rotating speeds.Mixed slurry is entered Row spray drying, obtains graininess composite granule.
Powdery intermediate product and 1kg medium temperature coal pitch obtained by the above-mentioned spray drying of 2kg are taken, it is hot at a temperature of 120-140 DEG C Kneading 2h；By kneading product, hot roller process, the rubber into about 2mm thickness are filled at 120-140 DEG C, and powder is broken into after cooling Material；Powder body material is put into rubber package set again, isostatic pressing 10 minutes under 200MPa pressure, are obtained in isostatic pressing machine Graphite/nano-silicon/pitch bulk green compact；Then after sieving being crushed into graphite/nano-silicon/pitch green compact, it is put into mechanical fusion In machine under 45m/s linear velocity mechanical fusion 30min, obtain graphite/nano-silicon/pitch composite particles；Protected in inert atmosphere Lower 900 DEG C are protected to calcine 4 hours；The silicon-carbon composite cathode material of silicone content 33% is obtained after breaing up and sieving.
Embodiment 5：
To take 2kg median particle diameters be 3 μm, silicone content is the micron silica flour more than 99%, is added in 18kg alcohol solvents, is surpassed After sound disperses 30min, pour into ultra-fine ball mill cavity.A diameter of 0.3mm zirconia ball is used as ball-milling medium, ratio of grinding media to material (mass ratio) is 10:1, ball milling 10 hours under 1800rpm rotating speed, obtain nano-silicon dispersion liquid.Into nano-silicon dispersion liquid 3.4kg flake graphites are added, uniform mixed slurry is obtained after ball milling is scattered 1 hour under 1000rpm rotating speeds.Mixed slurry is entered Row spray drying, obtains graininess composite granule.
Powdery intermediate product and 0.88kg coal tar pitchs obtained by the above-mentioned spray drying of 2kg are taken, at a temperature of 220-250 DEG C Hot kneading 2h；By kneading product, hot roller process, the rubber into about 2mm thickness are filled at 220-250 DEG C, and powder is broken into after cooling Body material；Powder body material is put into rubber package set again, isostatic pressing 10 minutes under 200MPa pressure, are obtained in isostatic pressing machine To graphite/nano-silicon/pitch bulk green compact；Then after sieving being crushed into graphite/nano-silicon/pitch green compact, it is put into machinery and melts In conjunction machine under 45m/s linear velocity mechanical fusion 20min, obtain graphite/nano-silicon/pitch composite particles；In inert atmosphere Lower 900 DEG C are protected to calcine 4 hours；The silicon-carbon composite cathode material of silicone content 33% is obtained after breaing up and sieving.
Embodiment 6：
To take 2kg median particle diameters be 3 μm, silicone content is the micron silica flour more than 99%, is added in 18kg alcohol solvents, is surpassed After sound disperses 30min, pour into ultra-fine ball mill cavity.A diameter of 0.3mm zirconia ball is used as ball-milling medium, ratio of grinding media to material (mass ratio) is 10:1, ball milling 10 hours under 1800rpm rotating speed, obtain nano-silicon dispersion liquid.Into nano-silicon dispersion liquid 5.5kg flake graphites are added, uniform mixed slurry is obtained after ball milling is scattered 1 hour under 1000rpm rotating speeds.Mixed slurry is entered Row spray drying, obtains graininess composite granule.
Powdery intermediate product and 1kg modified coal asphalts obtained by the above-mentioned spray drying of 2kg are taken, it is hot at a temperature of 160-180 DEG C Kneading 2h；By kneading product, hot roller process, the rubber into about 2mm thickness are filled at 160-180 DEG C, and powder is broken into after cooling Material；Powder body material is put into rubber package set again, isostatic pressing 10 minutes under 200MPa pressure, are obtained in isostatic pressing machine Graphite/nano-silicon/pitch bulk green compact；Then after sieving being crushed into graphite/nano-silicon/pitch green compact, it is put into mechanical fusion In machine under 45m/s linear velocity mechanical fusion 20min, obtain graphite/nano-silicon/pitch composite particles；Protected in inert atmosphere Lower 900 DEG C are protected to calcine 4 hours；The silicon-carbon composite cathode material of silicone content 22% is obtained after breaing up and sieving.
Comparative example 1：
To take 2kg median particle diameters be 3 μm, silicone content is the micron silica flour more than 99%, is added in 18kg alcohol solvents, is surpassed After sound disperses 30min, pour into ultra-fine ball mill cavity.A diameter of 0.3mm zirconia ball is used as ball-milling medium, ratio of grinding media to material (mass ratio) is 10:1, ball milling 10 hours under 1800rpm rotating speed, obtain nano-silicon dispersion liquid.Into nano-silicon dispersion liquid 3.4kg flake graphites are added, uniform mixed slurry is obtained after ball milling is scattered 1 hour under 1000rpm rotating speeds.Mixed slurry is entered Row spray drying, obtains graininess composite granule.
Powdery intermediate product and 1kg modified coal asphalts obtained by the above-mentioned spray drying of 2kg are taken, it is hot at a temperature of 160-180 DEG C Kneading 2h；By kneading product, hot roller process, the rubber into about 2mm thickness are filled at 160-180 DEG C, and powder is broken into after cooling Material；Powder body material is put into rubber package set again, isostatic pressing 10 minutes under 200MPa pressure, are obtained in isostatic pressing machine Graphite/nano-silicon/pitch bulk green compact；Then after sieving being crushed into graphite/nano-silicon/pitch green compact, protected in inert atmosphere Lower 900 DEG C are protected to calcine 4 hours；The silicon-carbon composite cathode material of silicone content 33% is obtained after breaing up and sieving.
Comparative example 2：
To take 2kg median particle diameters be 3 μm, silicone content is the micron silica flour more than 99%, is added in 18kg alcohol solvents, is surpassed After sound disperses 30min, pour into ultra-fine ball mill cavity.A diameter of 0.3mm zirconia ball is used as ball-milling medium, ratio of grinding media to material (mass ratio) is 10:1, ball milling 10 hours under 1800rpm rotating speed, obtain nano-silicon dispersion liquid.Into nano-silicon dispersion liquid 3.4kg flake graphites are added, uniform mixed slurry is obtained after ball milling is scattered 1 hour under 1000rpm rotating speeds.Mixed slurry is entered Row spray drying, obtains graininess composite granule.
Powdery intermediate product and 780gPVP binding agents and appropriate aqueous solvent obtained by the above-mentioned spray drying of 2kg are taken, normal The lower kneading 2h of temperature；After the drying of kneading product, crushing；Again by powder body material under 200MPa pressure isostatic pressing 10 minutes, Obtain block green compact；Then green compact are crushed, after sieving, is put into mechanical fusion machine the mechanical fusion under 45m/s linear velocity 20min, obtain composite particles；Calcined 4 hours for 900 DEG C under inert atmosphere protection；Silicone content is obtained after breaing up and sieving 33% silicon-carbon composite cathode material.
Comparative example 3：
To take 2kg median particle diameters be 3 μm, silicone content is the micron silica flour more than 99%, is added in 18kg alcohol solvents, is surpassed After sound disperses 30min, pour into ultra-fine ball mill cavity.A diameter of 0.3mm zirconia ball is used as ball-milling medium, ratio of grinding media to material (mass ratio) is 10:1, ball milling 10 hours under 1800rpm rotating speed, obtain nano-silicon dispersion liquid.Into nano-silicon dispersion liquid 3.4kg flake graphites are added, uniform mixed slurry is obtained after ball milling is scattered 1 hour under 1000rpm rotating speeds.Mixed slurry is entered Row spray drying, obtains graininess composite granule.
Powdery intermediate product and 1kg phenolic resin and appropriate alcohol solvent obtained by the above-mentioned spray drying of 2kg are taken, normal The lower kneading 2h of temperature；After the drying of kneading product, crushing；Again by powder body material under 200MPa pressure isostatic pressing 10 minutes, Obtain graphite/nano-silicon/phenolic resin bulk green compact；Then graphite/pitch/phenolic resin green compact are crushed, after sieving, be put into In mechanical fusion machine under 45m/s linear velocity mechanical fusion 20min, obtain composite particles；900 DEG C under inert atmosphere protection Calcining 4 hours；The silicon-carbon composite cathode material of silicone content 33% is obtained after breaing up and sieving.
Embodiment 1-6 and comparative example 1-3 prepares electrode and test material chemical property, test knot using following methods Fruit is as shown in table 1.
By silicon-carbon composite cathode material, conductive agent and binding agent by mass percentage 86:6:8 ratio is dissolved in solvent In, solid content 30%.Wherein binding agent uses mass ratio as 1:1 sodium carboxymethylcellulose (CMC, the 2wt%CMC aqueous solution) Butadiene-styrene rubber (SBR, the 50wt%SBR aqueous solution) compound water-based binder.Again plus 0.8wt% oxalic acid as etching copper foil acid Property material, obtains uniform sizing material after being sufficiently stirred.Coated on 10 μm of copper foils, after drying 4h at room temperature, with a diameter of 14 The drift of millimeter is washed into pole piece, in 100kg/cm-2Pressure lower sheeting, it is put into 120 DEG C of vacuum drying ovens and dries 8 hours.
Pole piece is transferred in glove box, uses metal lithium sheet as negative pole, Celgard2400 barrier films, 1mol/L LiPF6/ EC+DMC+EMC+2%VC (v/v/v=1:1:1) electrolyte, CR2016 battery cases assembling button cell.In Wuhan gold The charge-discharge test of constant current, the cycle charge-discharge under 0.2C multiplying powers, discharge and recharge are carried out on promise LandCT2001A battery test systems Blanking voltage is relative to Li/Li+For 0.005-2V.
The performance test results of the high-tap density silicon-carbon cathode material of table 1.
As can be seen from the table, obtained by the preparation method of the silicon-carbon cathode material comprising mechanical fusion processing step The tap density of silicon-carbon composite cathode material is improved, and specific surface area reduces, and first all coulombic efficiencies of material and circulation are steady It is qualitative to be obtained for larger raising.
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or Among changing still in the protection domain of the invention.

Claims (10)

1. a kind of preparation method of high performance silicon carbon negative pole material, comprises the following steps：
(1) silicon is disperseed to obtain nano-silicon dispersion liquid by liquid phase ball milling in a solvent, then adds graphite and pass through liquid phase ball milling Realize that nano-silicon mixes with the uniform of graphite；
(2) step (1) is mixed into gained slurry granulation and realizes that graphite/nano-silicon Composite is granulated；
(3) kneading-compacting-broken method is used to realize graphite/nano-silicon/pitch step (2) products therefrom and pitch Composite is granulated, then after being handled through mechanical fusion, and a step realizes the spheroidization and of graphite/nano-silicon/pitch composite particles Even cladding；
(4) after being carbonized, break up, sieve, the high performance silicon carbon compound cathode materials are obtained.
2. preparation method according to claim 1, it is characterised in that silicone content is not low in raw materials used silicon in step (1) In 99%；
Preferably, raw materials used silicon is the silica flour of micron silica flour, preferably 1-5 μm of median particle diameter；
Preferably, solvent is combination one kind or two or more in ethanol, methanol, isopropanol, n-butanol, acetone, toluene；
Preferably, the mass ratio of raw materials used silicon and solvent is 1:5-15, preferably 1:9.
3. preparation method according to claim 1 or 2, it is characterised in that ball-milling medium is zirconia ball in step (1), Preferably diameter 0.1-0.5mm zirconia ball；
Preferably, the ball material mass ratio of ball milling is 5-15 when preparing nano-silicon dispersion liquid:1, preferably 10:1；
Preferably, the rotating speed of ball milling is 1500-2000rpm when preparing nano-silicon dispersion liquid, and the time of ball milling is more than 5 hours.
4. according to the preparation method described in claim any one of 1-3, it is characterised in that in step (1) graphite with it is raw materials used The mass ratio of silicon is 1-3:1, preferably 1.7:1；
Preferably, the rotating speed of ball milling is 500-1500rpm after addition graphite, and the time of ball milling is more than 0.5 hour；
Preferably, the ratio of grinding media to material of ball milling is 3-15 after addition graphite:1；
Preferably, the method using spray drying is granulated in step (2).
5. according to the preparation method described in claim any one of 1-4, it is characterised in that graphite/nano-silicon/drip in step (3) Blue or green Composite granulation process is：Step (2) products therefrom and hot-rolling pressure after the hot kneading of pitch, are broken into powder material after cooling Material；Powder body material isostatic pressing is obtained into graphite/nano-silicon/pitch bulk green compact again；Then by the broken sieving of green compact.
6. preparation method according to claim 5, it is characterised in that pitch be more than 60 DEG C of softening temperature coal tar pitch or Asphalt；
Preferably, the mass ratio of step (2) products therefrom and pitch is 1-4:1, preferably 2:1.
7. the preparation method according to claim 5 or 6, it is characterised in that the temperature of hot kneading is 100-300 DEG C, preferably For 120-250 DEG C, the time is more than 1h, preferably 2h；
Preferably, the temperature of hot-rolling pressure is 100-300 DEG C, preferably 120-250 DEG C；
Preferably, pressure during isostatic pressing is 150-300MPa, and the time of isostatic pressing is more than 5min.
8. according to the preparation method described in claim any one of 5-7, it is characterised in that linear velocity during mechanical fusion is 10- 50m/s, the time of mechanical fusion is 3-60min, preferably 15-30min.
9. according to the preparation method described in claim any one of 1-8, it is characterised in that carbonization is in inert atmosphere in step (4) Protection is lower to be carried out, and the temperature of carbonization is 800-1000 DEG C, and preferably 900 DEG C, the time of carbonization is more than 2h, preferably 4h.
A kind of 10. any one of claim 1-9 silicon-carbon composite cathode materials made from the preparation method.
CN201711128166.1A 2017-11-15 2017-11-15 High-performance silicon-carbon negative electrode material and preparation method thereof Active CN107785560B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711128166.1A CN107785560B (en) 2017-11-15 2017-11-15 High-performance silicon-carbon negative electrode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711128166.1A CN107785560B (en) 2017-11-15 2017-11-15 High-performance silicon-carbon negative electrode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107785560A true CN107785560A (en) 2018-03-09
CN107785560B CN107785560B (en) 2020-07-21

Family

ID=61433238

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711128166.1A Active CN107785560B (en) 2017-11-15 2017-11-15 High-performance silicon-carbon negative electrode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107785560B (en)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109216690A (en) * 2018-11-01 2019-01-15 湖北融通高科先进材料有限公司 A kind of high capacity Si-C composite material and preparation method thereof and lithium ion battery
CN109346681A (en) * 2018-08-17 2019-02-15 福建翔丰华新能源材料有限公司 A kind of nuclear shell structure nano silicon-MXene composite negative pole material and preparation method thereof
CN110429272A (en) * 2019-08-19 2019-11-08 上海昱瓴新能源科技有限公司 The silicon-carbon composite cathode material and preparation method thereof of one type dragon fruit structure
CN110993926A (en) * 2020-01-09 2020-04-10 郑州中科新兴产业技术研究院 Preparation method of high-stability silicon-carbon composite material for lithium ion battery
CN111106333A (en) * 2019-12-12 2020-05-05 新奥石墨烯技术有限公司 Silicon-carbon negative electrode material and preparation method and application thereof
CN111224078A (en) * 2018-11-27 2020-06-02 广州汽车集团股份有限公司 Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery negative electrode
CN111354937A (en) * 2020-04-21 2020-06-30 隆能科技(南通)有限公司 Preparation method of core-shell structure high-capacity silicon-carbon composite negative electrode material for lithium ion battery
CN111653745A (en) * 2020-05-28 2020-09-11 长沙矿冶研究院有限责任公司 Silicon-carbon negative electrode precursor material, silicon-carbon negative electrode material and preparation method thereof
CN111755681A (en) * 2020-07-06 2020-10-09 马鞍山科达普锐能源科技有限公司 Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof
CN112133894A (en) * 2020-09-03 2020-12-25 深圳石墨烯创新中心有限公司 Negative electrode material for lithium battery and preparation method of material
CN112290006A (en) * 2020-11-23 2021-01-29 山东硅纳新材料科技有限公司 Simple and efficient preparation method of silicon-carbon anode material
WO2021040932A1 (en) * 2019-08-29 2021-03-04 Novonix Battery Testing Services Inc. Improved microgranulation methods and product particles therefrom
WO2021113919A1 (en) * 2019-12-13 2021-06-17 Sicona Battery Technologies Pty Ltd Anode for lithium-ion battery and method of fabricating same
CN113161521A (en) * 2021-03-10 2021-07-23 广东海洋大学 Natural graphite-based silicon-carbon composite negative electrode material and preparation method and application thereof
CN113169321A (en) * 2018-11-30 2021-07-23 株式会社Posco Negative electrode active material for lithium secondary battery, method for preparing same, and lithium secondary battery comprising same
CN113644252A (en) * 2021-08-04 2021-11-12 西北工业大学 Silicon-carbon negative electrode material and preparation method thereof
WO2021238600A1 (en) * 2020-05-26 2021-12-02 深圳市翔丰华科技股份有限公司 Silicon-carbon negative electrode material for lithium ion battery and preparation method therefor
CN114031081A (en) * 2021-08-18 2022-02-11 中钢热能金灿新能源科技(湖州)有限公司 Isotropic silicon carbon negative electrode material and preparation method and application thereof
CN114275760A (en) * 2021-12-22 2022-04-05 江西紫宸科技有限公司 Silicon-carbon composite material and preparation method and application thereof
CN114388755A (en) * 2021-12-14 2022-04-22 鞍钢化学科技有限公司 Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof
CN114447294A (en) * 2021-12-28 2022-05-06 长沙矿冶研究院有限责任公司 Silicon-carbon composite negative electrode material with high compact structure and preparation method thereof
CN115000368A (en) * 2022-05-30 2022-09-02 孟垂舟 Preparation method of high-tap-density silicon-carbon composite material, silicon-carbon composite material and application
CN115050933A (en) * 2022-05-30 2022-09-13 孟垂舟 Silicon-carbon composite material and preparation method and application thereof
EP3966883A4 (en) * 2019-05-08 2023-02-08 Eocell Limited Silicon carbon nanocomposite (scn) material, fabrication process therefor, and use thereof in an anode electrode of a lithium ion battery
WO2023039074A1 (en) * 2021-09-08 2023-03-16 Koppers Delaware, Inc. Dispersion of coal tar pitch for coating graphitic materials and use in li-ion battery electrode production

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102569726A (en) * 2010-12-30 2012-07-11 中国电子科技集团公司第十八研究所 Method for preparing lithium ion battery anode material coated with metal ions
CN102891297A (en) * 2012-11-10 2013-01-23 江西正拓新能源科技有限公司 Silicon-carbon composite material for lithium ion battery and preparation method thereof
CN106257716A (en) * 2016-08-30 2016-12-28 浙江超威创元实业有限公司 The preparation method of a kind of silicon-carbon composite cathode material and lithium ion battery
CN106531980A (en) * 2015-11-17 2017-03-22 宁波杉杉新材料科技有限公司 Negative electrode material for lithium-ion battery and preparation method and application of negative electrode material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102569726A (en) * 2010-12-30 2012-07-11 中国电子科技集团公司第十八研究所 Method for preparing lithium ion battery anode material coated with metal ions
CN102891297A (en) * 2012-11-10 2013-01-23 江西正拓新能源科技有限公司 Silicon-carbon composite material for lithium ion battery and preparation method thereof
CN106531980A (en) * 2015-11-17 2017-03-22 宁波杉杉新材料科技有限公司 Negative electrode material for lithium-ion battery and preparation method and application of negative electrode material
CN106257716A (en) * 2016-08-30 2016-12-28 浙江超威创元实业有限公司 The preparation method of a kind of silicon-carbon composite cathode material and lithium ion battery

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109346681A (en) * 2018-08-17 2019-02-15 福建翔丰华新能源材料有限公司 A kind of nuclear shell structure nano silicon-MXene composite negative pole material and preparation method thereof
CN109216690A (en) * 2018-11-01 2019-01-15 湖北融通高科先进材料有限公司 A kind of high capacity Si-C composite material and preparation method thereof and lithium ion battery
CN111224078A (en) * 2018-11-27 2020-06-02 广州汽车集团股份有限公司 Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery negative electrode
CN113169321A (en) * 2018-11-30 2021-07-23 株式会社Posco Negative electrode active material for lithium secondary battery, method for preparing same, and lithium secondary battery comprising same
EP3966883A4 (en) * 2019-05-08 2023-02-08 Eocell Limited Silicon carbon nanocomposite (scn) material, fabrication process therefor, and use thereof in an anode electrode of a lithium ion battery
CN110429272A (en) * 2019-08-19 2019-11-08 上海昱瓴新能源科技有限公司 The silicon-carbon composite cathode material and preparation method thereof of one type dragon fruit structure
WO2021040932A1 (en) * 2019-08-29 2021-03-04 Novonix Battery Testing Services Inc. Improved microgranulation methods and product particles therefrom
CN111106333A (en) * 2019-12-12 2020-05-05 新奥石墨烯技术有限公司 Silicon-carbon negative electrode material and preparation method and application thereof
WO2021113919A1 (en) * 2019-12-13 2021-06-17 Sicona Battery Technologies Pty Ltd Anode for lithium-ion battery and method of fabricating same
WO2021113920A1 (en) * 2019-12-13 2021-06-17 Sicona Battery Technologies Pty Ltd Multifunctional polymer binder for anode and method of producing same
CN110993926A (en) * 2020-01-09 2020-04-10 郑州中科新兴产业技术研究院 Preparation method of high-stability silicon-carbon composite material for lithium ion battery
CN111354937A (en) * 2020-04-21 2020-06-30 隆能科技(南通)有限公司 Preparation method of core-shell structure high-capacity silicon-carbon composite negative electrode material for lithium ion battery
CN111354937B (en) * 2020-04-21 2022-03-11 隆能科技(南通)有限公司 Preparation method of core-shell structure high-capacity silicon-carbon composite negative electrode material for lithium ion battery
WO2021238600A1 (en) * 2020-05-26 2021-12-02 深圳市翔丰华科技股份有限公司 Silicon-carbon negative electrode material for lithium ion battery and preparation method therefor
CN111653745A (en) * 2020-05-28 2020-09-11 长沙矿冶研究院有限责任公司 Silicon-carbon negative electrode precursor material, silicon-carbon negative electrode material and preparation method thereof
CN111755681A (en) * 2020-07-06 2020-10-09 马鞍山科达普锐能源科技有限公司 Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof
CN112133894A (en) * 2020-09-03 2020-12-25 深圳石墨烯创新中心有限公司 Negative electrode material for lithium battery and preparation method of material
CN112290006A (en) * 2020-11-23 2021-01-29 山东硅纳新材料科技有限公司 Simple and efficient preparation method of silicon-carbon anode material
CN113161521A (en) * 2021-03-10 2021-07-23 广东海洋大学 Natural graphite-based silicon-carbon composite negative electrode material and preparation method and application thereof
CN113161521B (en) * 2021-03-10 2022-11-01 广东海洋大学 Natural graphite-based silicon-carbon composite negative electrode material and preparation method and application thereof
CN113644252A (en) * 2021-08-04 2021-11-12 西北工业大学 Silicon-carbon negative electrode material and preparation method thereof
CN114031081A (en) * 2021-08-18 2022-02-11 中钢热能金灿新能源科技(湖州)有限公司 Isotropic silicon carbon negative electrode material and preparation method and application thereof
CN114031081B (en) * 2021-08-18 2023-09-01 湖州启源金灿新能源科技有限公司 Isotropic silicon-carbon negative electrode material and preparation method and application thereof
WO2023039074A1 (en) * 2021-09-08 2023-03-16 Koppers Delaware, Inc. Dispersion of coal tar pitch for coating graphitic materials and use in li-ion battery electrode production
CN114388755A (en) * 2021-12-14 2022-04-22 鞍钢化学科技有限公司 Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof
CN114275760A (en) * 2021-12-22 2022-04-05 江西紫宸科技有限公司 Silicon-carbon composite material and preparation method and application thereof
CN114447294A (en) * 2021-12-28 2022-05-06 长沙矿冶研究院有限责任公司 Silicon-carbon composite negative electrode material with high compact structure and preparation method thereof
CN114447294B (en) * 2021-12-28 2024-03-22 长沙矿冶研究院有限责任公司 Silicon-carbon composite negative electrode material with high compact structure and preparation method thereof
CN115000368A (en) * 2022-05-30 2022-09-02 孟垂舟 Preparation method of high-tap-density silicon-carbon composite material, silicon-carbon composite material and application
CN115050933A (en) * 2022-05-30 2022-09-13 孟垂舟 Silicon-carbon composite material and preparation method and application thereof
CN115050933B (en) * 2022-05-30 2023-12-15 孟垂舟 Silicon-carbon composite material and preparation method and application thereof
CN115000368B (en) * 2022-05-30 2023-12-15 孟垂舟 Preparation method of high-tap-density silicon-carbon composite material, silicon-carbon composite material and application

Also Published As

Publication number Publication date
CN107785560B (en) 2020-07-21

Similar Documents

Publication Publication Date Title
CN107785560A (en) A kind of high performance silicon carbon negative pole material and preparation method thereof
CN105655564B (en) SiOx/ C composite negative pole material and its preparation method and application
US20210384500A1 (en) Silicon oxide/carbon composite negative electrode material and preparation method therefor, and lithium-ion battery
CN106025222B (en) A kind of preparation method of the silicon of cladding/carbon graphite composite negative pole material
CN108123111A (en) A kind of lithium ion battery silicon substrate composite negative pole material, its preparation method and the negative electrode of lithium ion battery comprising the material
CN106784640B (en) Silicon-based composite negative electrode material for lithium ion battery, preparation method of silicon-based composite negative electrode material and lithium ion battery negative electrode containing silicon-based composite negative electrode material
CN107785541B (en) Silicon-carbon composite material for lithium ion battery and preparation method thereof
KR102344143B1 (en) Predoping method for lithium, lithium­predoped electrode, and electricity storage device
CN111224078A (en) Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery negative electrode
CN106711461A (en) Spherical porous silicon/carbon composite material as well as preparation method and application thereof
CN102593434B (en) Composite graphite particles for lithium secondary battery and preparation method thereof
CN106848264A (en) A kind of porous silicon oxide lithium ion battery negative material and preparation method thereof
CN105098184A (en) Preparation method of composite graphite, composite graphite and lithium ion battery
CN103078090A (en) Lithium ion power battery composite cathode material and its preparation method
CN111725504B (en) Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof
JP5625007B2 (en) Positive electrode for lithium ion secondary battery, lithium ion secondary battery and battery module
CN109704323A (en) Electrode material and secondary battery
CN105489893A (en) Graphite anode material for lithium-ion battery and preparation method of graphite anode material
CN101908627B (en) Cathode material of lithium ion secondary battery and preparation method thereof
JP2022534241A (en) Silica particles for electrode material and its production method and application
CN112652770A (en) Silicon-carbon negative electrode material with low specific surface area and preparation method thereof
WO2016169150A1 (en) Method for graphite fine powder to be doped and used as negative electrode material
JP2015060799A (en) Electrode material for lithium ion battery and method for producing the same, electrode for lithium ion battery, and lithium ion battery
CN105789627A (en) Preparation method of high-performance graphite negative electrode material for lithium ion battery
KR101944384B1 (en) Lithium ion secondary battery and method for manufacturing the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant