CN108281634A - A kind of method and its application of graphene coated graphite negative material of lithium ion battery - Google Patents

A kind of method and its application of graphene coated graphite negative material of lithium ion battery Download PDF

Info

Publication number
CN108281634A
CN108281634A CN201810076397.0A CN201810076397A CN108281634A CN 108281634 A CN108281634 A CN 108281634A CN 201810076397 A CN201810076397 A CN 201810076397A CN 108281634 A CN108281634 A CN 108281634A
Authority
CN
China
Prior art keywords
graphite
solvent
lithium ion
ion battery
graphene
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
Application number
CN201810076397.0A
Other languages
Chinese (zh)
Inventor
高坡
瞿研
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.)
SIXTH ELEMENT (CHANGZHOU) Ltd
Original Assignee
SIXTH ELEMENT (CHANGZHOU) 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 SIXTH ELEMENT (CHANGZHOU) Ltd filed Critical SIXTH ELEMENT (CHANGZHOU) Ltd
Priority to CN201810076397.0A priority Critical patent/CN108281634A/en
Publication of CN108281634A publication Critical patent/CN108281634A/en
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention discloses a kind of method of graphene coated graphite negative material of lithium ion battery, includes the following steps:(1) graphite ultrasonic disperse is obtained into graphite suspension in solvent;(2) graphite oxide ultrasonic dissolution is obtained into graphene oxide solution in solvent;(3) mass ratio for pressing graphene oxide and graphite is 0.01~0.3:1, graphite suspension is added in graphene oxide solution, then ultrasonic mixing removes solvent, obtain dry solid powder;(4) under an inert atmosphere, the solid powder obtained by step (3) handles 1~4h in 600~1000 DEG C, cooling to obtain the graphite negative material of lithium ion battery of graphene coated.This method is simple and practicable, and energy consumption is low, and environmental-friendly, at low cost, covered effect is good, and purity is high, suitable for large batch of industrialized production.Without adding conductive agent when as lithium ion battery negative material, and cycle performance is very excellent, and first charge discharge efficiency is up to 90%.

Description

A kind of method and its application of graphene coated graphite negative material of lithium ion battery
The application be the applying date be on April 21st, 2015, application No. is 201510190383.8 applications for a patent for invention " one The divisional application of the method for kind graphene coated graphite negative material of lithium ion battery and application ".
Technical field
The invention belongs to field of lithium ion battery, and in particular to a kind of graphene coated graphite negative material of lithium ion battery Method and its application.
Background technology
Lithium ion battery has entered functionization the seventies as a kind of emerging power supply, because of its, electricity high with energy density The advantages that cell voltage is high, storage life is long, is widely used on various portable electronic products and electric tool, especially exists It plays an important role in terms of electric vehicle (EV) and hybrid-electric car (HEV) power supply.
Negative material is one of critical material of lithium ion battery, and carbonaceous material is people's early start studies and apply In the material of negative electrode of lithium ion battery, carbonaceous materials are still received significant attention so far and are mainly had the following advantages:Specific capacity is high (200~400mAh/g), electrode potential is low, cycle efficieny height (>95%) it, has extended cycle life.It is negative that more carbonaceous is studied at present Pole material has graphite, mesocarbon microspheres (MCMB), height ratio capacity carbide, petroleum coke etc..These carbonaceous materials respectively have its excellent Disadvantage, in recent years, as that studies carbonaceous material deepens continuously, it has been found possible to by being tied to all kinds of carbonaceous materials Structure adjusts, and such as forms nano grade pore structure, is surface modified and modification or doping treatment.It may make lithium wherein Insertion/deintercalation not only can stoichiometrically LiC6It carries out, and also non-stoichiometric insertion/deintercalation, to make carbonaceous Material specific capacity is more than the theoretical value 372mAhg of graphite, reaches 700g~1000mAh/g.Meanwhile using nanometer carbon material, A new research hotspot is had become as lithium ion battery negative material.But because source and the preparation of nanometer carbon material Method is different.Structure has very big difference and causes to be very different in its embedding lithium capacity and embedding lithium mechanism.
Graphene is the basic unit for constituting other carbon material structures, and graphene wraps up the fullerene that can form zero dimension, One-dimensional carbon nanotube can be formed by curling, and superposition can form three-dimensional graphite.The theoretical specific surface area of grapheme material is high Up to 2600m2/ g has heat conductivility outstanding and ultimate strength, and the electron mobility of high speed at room temperature, these are excellent Property makes it have very big development prospect in terms of energy storage.But as a kind of brand-new material graphene itself agglomeration traits It can not solve well always.
Current commercialized graphite cathode material has more highly oriented layer structure, sensitive to electrolyte, with solvent phase Capacitive is poor;The high current charge-discharge ability of graphite cathode material is relatively low, causes power performance poor.Simultaneously as graphite Interlamellar spacing is less than lithium and is inserted into the compound between graphite layers Li formed after graphite liningsxC6Crystal face interlamellar spacing (d002=0.37nm), During charge and discharge cycles, graphite layers are away from changing greatly;And also occur that lithium is inserted into graphite layers jointly with organic solvent And the further decomposition of organic solvent.It is easy to cause that graphite linings are gradually peeled off, graphite particle is burst apart and dusting, to drop Low negative material cycle life.
Invention content
For the above problem of the prior art, it is negative that the object of the present invention is to provide a kind of lithium ion graphite of graphene coated The preparation method of pole material.This method is simple and practicable, and energy consumption is low, and environmental-friendly, at low cost, covered effect is good, suitable for large quantities of The industrialized production of amount.
A kind of method of graphene coated graphite negative material of lithium ion battery, includes the following steps:
(1) graphite ultrasonic disperse is obtained into graphite suspension in solvent;
(2) graphite oxide ultrasonic dissolution is obtained into graphene oxide solution in solvent;
(3) mass ratio for pressing graphene oxide and graphite is (0.01~0.3):1, graphite is added in graphene oxide solution Suspension obtains mixed liquor;
(4) and then solvent is removed, obtains dry solid powder;
(5) under an inert atmosphere, the solid powder obtained by step (4) handles 1~4h in 600~1000 DEG C, and cooling to obtain the final product To the graphite negative material of lithium ion battery of graphene coated.
Further, the solvent described in step (1) and/or step (2) is water, ethyl alcohol and/or acetone.
Further, the solvent in the step (1) is water and ethyl alcohol, and graphite ultrasonic agitation is first distributed to a small amount of ethyl alcohol In, then water is added, ultrasonic disperse obtains graphite suspension.In the step (1), contain in graphite suspension described in every 100mL The amount of graphite is 10g.
Further, the solvent in the step (2) is water.In the step (2), it is configured to per 0.2g graphene oxides Graphene oxide solution described in 50mL.
In the step (3), under stiring, slowly graphene oxide water solution is added in graphite suspension, is surpassed Sound 30min is further continued for stirring 2 hours, obtains mixed liquor.
Further, the process of step (4) removing solvent includes:Filtering, drying;Alternatively, evaporation, drying;Or spraying is dry It is dry.
Preferably, the method for step (4) the removing solvent is:The mixed liquor that first step 3 is obtained is using filtering, steaming Hair or the preliminary removal solvent of spray drying, obtained solid powder, then solid powder is first dried overnight in draught cupboard, Then 10 hours dry in 50 DEG C in vacuum drying chamber.
Further, step (5) described inert atmosphere is nitrogen, argon gas and/or helium.
Further, in step (5), temperature rises to 600~1000 DEG C with the speed of 1~3 DEG C/min.It is preferred that with 2 DEG C/min Speed rise to 800 DEG C.
It is not necessary that any conductive agent is added when according to material obtained by the above method as lithium ion battery negative material, and follow Ring performance is very excellent, and first charge discharge efficiency is up to 90%.
Main advantages of the present invention are:
1, graphene oxide removes oxygen-containing group at high temperature, woth no need to separately plus reducing agent, will not introduce any metal from Son makes product keep very high degree of purity;
2, graphene layer can be effectively coated on to the surface of graphite cathode material, covered effect is good;
3, without adding conductive agent, and cyclicity when the material of present invention gained is used as lithium ion battery negative material Can be very excellent, first charge discharge efficiency is up to 90% or more;
4, the method for the present invention is simple for process, and mild condition, technological parameter is easily-controllable, and energy consumption is low, environmentally friendly, is conducive to work Industryization mass produces.
Description of the drawings
Fig. 1 is the scanning electron microscopic picture of 1 resulting materials of embodiment.
Fig. 2 is first charge-discharge curve of 1 resulting materials of embodiment as lithium ion battery negative material, and voltage range is 0.005~2.000V, 0.1C.
Fig. 3 is efficiency and cycle performance of 1 resulting materials of embodiment as lithium ion battery negative material.
Specific implementation mode
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
1. weighing 10g graphite samples (natural spherical plumbago) in 250ml beakers, a small amount of ethyl alcohol is added, with ultrasonic agitation Dispersion, then water is added, ultrasound is made into the graphite suspension of 100ml;
2. weighing 0.2g graphite oxides in 100ml beakers, add water, under ultrasonic agitation, is made into the graphite oxide of 50ml Aqueous solution;
3. under stiring, slowly 50ml graphene oxide water solutions are added in 100ml graphite suspensions, then surpass Sound 30 minutes is further continued for stirring 2 hours, obtains mixed liquor;
4. filtering above-mentioned mixed liquor, obtained solid powder is first dried overnight in draught cupboard, then in vacuum drying chamber In it is 10 hours dry in 50 DEG C;
5. dried solid powder sample is put into tube furnace, it is passed through N2(flow velocity 50ml/min), then with 2 DEG C/ Min rises to 800 DEG C, is sintered 2 hours postcoolings at such a temperature to room temperature to get to the graphite composite material of graphene coated. As seen from Figure 1, thin graphene is wrapped in graphite particle surface, has good being evenly coated property.
(300 turns/min) ball milling is after 2 hours under the low speed for the composite material of 1 gained of embodiment, by itself and Kynoar (PVDF) 92 are pressed:8 mass ratio is made into film after slurry, and cathode selects metal lithium sheet, and electrolyte is that electrolyte is 1mol/L's LiPF6/ ethylene carbonate+diethyl carbonate (1:1), diaphragm is polypropylene microporous film, and button cell is made, and evaluates its conduct The performance of lithium cell negative pole material.
Fig. 2 is the first charge-discharge curve of button cell, and charging/discharging voltage section is 0.005~2.000V, and electric current is (1C=372mAh/g) is arranged in 0.1C, and test temperature is 20 DEG C, graphene modified graphite cathode material charge and discharge specific capacity for the first time Respectively:372mAh/g (charging) and 410mAh/g (electric discharge), efficiency 90.7%, and non-modified graphite cathode material is for the first time Charge and discharge specific capacity is respectively:350mAh/g (charging) and 393mAh/g (electric discharge), efficiency 89%.
Fig. 3 is the efficiency and cycle performance figure of battery, as shown, after 20 circle of 0.3C cycles, capacity retention ratio 98%.
Embodiment 2
It is 900 DEG C to change sintering temperature, other conditions such as embodiment 1.
Embodiment 3
It is 4 hours to change sintering time, other conditions such as embodiment 1.
Embodiment 3
The quality for changing graphite oxide is 1.06g, other conditions such as embodiment 1.
Embodiment 4
1. weighing 10g graphite samples (business electrographite) in 250ml beakers, a small amount of ethyl alcohol is added, with ultrasonic agitation Dispersion, then water is added, ultrasound is made into the graphite suspension of 100ml;
2. weighing 0.2g graphite oxides in 100ml beakers, add water, under ultrasonic agitation, is made into the graphite oxide of 50ml Aqueous solution;
3. under stiring, slowly 50ml graphene oxide water solutions are added in 100ml graphite suspensions, then surpass Sound 30 minutes is further continued for stirring 2 hours, obtains mixed liquor;
4. after carefully removing the evaporation of the solvent of above-mentioned mixed liquor, obtained solid powder is again in vacuum drying chamber in 50 DEG C dry 10 hours;
5. dried solid powder sample is put into tube furnace, it is passed through N2(flow velocity 50ml/min), then with 2 DEG C/ Min rises to 800 DEG C, keeps 2 hours postcoolings to room temperature to get to the graphite composite material of graphene coated at such a temperature.
Embodiment 5
1. weighing 10g graphite samples (natural spherical plumbago) in 250ml beakers, a small amount of ethyl alcohol is added, with ultrasonic agitation Dispersion, then water is added, ultrasound is made into the graphite suspension of 100ml;
2. weighing 0.2g graphite oxides in 100ml beakers, add water, under ultrasonic agitation, is made into the graphite oxide of 50ml Aqueous solution;
3. under stiring, slowly 50ml graphene oxide water solutions are added in 100ml graphite suspensions, then surpass Sound 30 minutes is further continued for stirring 2 hours, obtains mixed liquor;
4. above-mentioned mixed liquor is handled using spray drying process, obtained solid powder first stays overnight drying in draught cupboard, so 50 DEG C of dryings 10 hours in vacuum drying chamber afterwards;
5. dried solid powder sample is put into tube furnace, it is passed through N2(flow velocity 50ml/min), then with 2 DEG C/ Min rises to 800 DEG C, keeps 2 hours postcoolings to room temperature to get to the graphite composite material of graphene coated at such a temperature.
The ion cathode material lithium of graphene coated graphite made from embodiment 2,3,4,5 is similar to 1 pattern of embodiment, material Excellent charging and discharging capacity and cycle performance are embodied after material assembly battery.
Conclusion:
The ion cathode material lithium product purity of graphene coated graphite made from method provided by the invention is high.Material fills With embodying excellent charging and discharging capacity and cycle performance after battery.Simple production process is easy, and energy consumption is low, environment friend It is good, it is at low cost, suitable for large batch of industrialized production.
It should be understood that for those of ordinary skills, it can be modified or changed according to the above description, And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.

Claims (10)

1. a kind of method of graphene coated graphite negative material of lithium ion battery, includes the following steps:
(1) graphite ultrasonic disperse is obtained into graphite suspension in solvent;
(2) graphite oxide ultrasonic dissolution is obtained into graphene oxide solution in solvent;
(3) mass ratio for pressing graphene oxide and graphite is (0.01~0.3):1, graphite is added in graphene oxide solution and is suspended Liquid obtains mixed liquor;
(4) and then solvent is removed, obtains dry solid powder;
(5) under an inert atmosphere, the solid powder obtained by step (4) handles 1~4h in 600~1000 DEG C, cooling to obtain stone The graphite negative material of lithium ion battery of black alkene cladding.
2. according to the method described in claim 1, it is characterized in that, molten described in the step (1) and/or the step (2) Agent is water, ethyl alcohol and/or acetone.
3. according to the method described in claim 2, it is characterized in that, the solvent in the step (1) is water and ethyl alcohol, first by stone Ink ultrasonic agitation is distributed in a small amount of ethyl alcohol, then adds water, and ultrasonic disperse obtains graphite suspension;
Preferably, in the step (1), the amount containing graphite is 10g in graphite suspension described in every 100mL.
4. according to the method described in claim 2, it is characterized in that, the solvent in the step (2) is water;
Preferably, in the step (2), graphene oxide solution described in 50mL is configured to per 0.2g graphene oxides.
5. according to the method described in claim 1, it is characterized in that, in the step (3), under stiring, will slowly aoxidize Graphene aqueous solution is added in graphite suspension, ultrasonic 30min, is further continued for stirring 2 hours, is obtained mixed liquor.
6. according to the method described in claim 1, it is characterized in that, the process that step (4) removes solvent includes:Filtering, drying; Alternatively, evaporation, drying;Or spray drying;
Preferably, the method for step (4) the removing solvent is:The mixed liquor that first step 3 is obtained using filtering, evaporation or The preliminary removal solvent of person's spray drying, obtained solid powder, then solid powder is first dried overnight in draught cupboard, then exist It is 10 hours dry in 50 DEG C in vacuum drying chamber.
7. according to the method described in claim 1, it is characterized in that, step (5) described inert atmosphere be nitrogen, argon gas and/or Helium.
8. according to the method described in claim 1, it is characterized in that, in step (5), temperature is risen to the speed of 1~3 DEG C/min 600~1000 DEG C, preferable temperature rises to 800 DEG C with the speed of 2 DEG C/min.
9. the material obtained according to any methods of claim 1-5.
10. application of the material described in claim 6 as lithium ion battery negative material.
CN201810076397.0A 2015-04-21 2015-04-21 A kind of method and its application of graphene coated graphite negative material of lithium ion battery Pending CN108281634A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810076397.0A CN108281634A (en) 2015-04-21 2015-04-21 A kind of method and its application of graphene coated graphite negative material of lithium ion battery

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810076397.0A CN108281634A (en) 2015-04-21 2015-04-21 A kind of method and its application of graphene coated graphite negative material of lithium ion battery
CN201510190383.8A CN104868106A (en) 2015-04-21 2015-04-21 Method for coating graphite anode material of lithium ion battery with graphene and application thereof

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201510190383.8A Division CN104868106A (en) 2015-04-21 2015-04-21 Method for coating graphite anode material of lithium ion battery with graphene and application thereof

Publications (1)

Publication Number Publication Date
CN108281634A true CN108281634A (en) 2018-07-13

Family

ID=53913784

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201810076397.0A Pending CN108281634A (en) 2015-04-21 2015-04-21 A kind of method and its application of graphene coated graphite negative material of lithium ion battery
CN201510190383.8A Pending CN104868106A (en) 2015-04-21 2015-04-21 Method for coating graphite anode material of lithium ion battery with graphene and application thereof

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201510190383.8A Pending CN104868106A (en) 2015-04-21 2015-04-21 Method for coating graphite anode material of lithium ion battery with graphene and application thereof

Country Status (1)

Country Link
CN (2) CN108281634A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109411723A (en) * 2018-10-16 2019-03-01 上海应用技术大学 A kind of preparation method of graphene/graphite lithium ion battery negative electrode material
CN109585820A (en) * 2018-11-23 2019-04-05 四川大学 Si-C composite material, preparation method, application and negative electrode of lithium ion battery
CN109802115A (en) * 2019-01-15 2019-05-24 江西星盈科技有限公司 Lithium ion battery and negative electrode material and preparation method thereof
CN112803024A (en) * 2021-01-18 2021-05-14 山东玉皇新能源科技有限公司 Regeneration method and application of waste lithium ion battery negative electrode graphite material
CN113955747A (en) * 2021-10-20 2022-01-21 北京化工大学常州先进材料研究院 Preparation method of graphene-coated natural graphite negative electrode material
CN114551830A (en) * 2022-02-21 2022-05-27 海城申合科技有限公司 Preparation method of graphene oxide coated artificial graphite lithium ion negative electrode material
CN114804094A (en) * 2022-04-15 2022-07-29 广东凯金新能源科技股份有限公司 Nitrogen-graphene doped composite graphite negative electrode material and preparation method thereof
CN115000371A (en) * 2022-06-06 2022-09-02 深圳材启新材料有限公司 Preparation method of graphene-coated graphite powder

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106486646A (en) * 2015-08-28 2017-03-08 张明东 Lithium ion battery negative material and preparation method thereof and lithium ion battery
CN105958069A (en) * 2016-05-27 2016-09-21 雅安乾润锂电池材料有限公司 Preparation method of graphite negative electrode material for lithium-ion battery
CN107507963A (en) * 2016-06-14 2017-12-22 宁波杉杉新材料科技有限公司 A kind of preparation method of graphene coated artificial plumbago negative pole material
TWI649916B (en) * 2017-01-12 2019-02-01 河南烯碳合成材料有限公司 Positive electrode of lithium ion battery
CN108346801B (en) * 2017-01-24 2020-07-17 河南烯碳合成材料有限公司 Positive electrode of lithium ion battery
CN108183208A (en) * 2017-12-24 2018-06-19 林荣铨 A kind of graphene/solid carbon ball lithium ion battery negative material preparation method and preparation method thereof
CN112320796B (en) * 2020-10-30 2022-04-05 浙江锂宸新材料科技有限公司 Preparation method for simply increasing graphite layer spacing
CN112886008A (en) * 2021-01-19 2021-06-01 青海凯金新能源材料有限公司 Carbon-coated graphite negative electrode material and preparation method thereof
CN115286952B (en) * 2022-08-30 2023-10-03 广东一纳科技有限公司 Graphene composite powder applied to electrophoretic paint, preparation method of graphene composite powder and electrophoretic paint

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102544459A (en) * 2012-01-09 2012-07-04 上海交通大学 Method for preparing graphene-coated carbon microsphere material by coating graphene oxide on carbon microsphere
CN102569810A (en) * 2011-12-30 2012-07-11 常州第六元素材料科技股份有限公司 Graphene modified lithium ion battery anode material and preparation method thereof
CN103050666A (en) * 2012-12-12 2013-04-17 中南大学 Preparation method of silicon and carbon-coated graphene composite cathode material
CN103985873A (en) * 2014-05-19 2014-08-13 陕西科技大学 Method of improving cycling stability of negative electrode material for lithium ion battery
CN104269543A (en) * 2014-10-09 2015-01-07 南京中储新能源有限公司 Graphene-cladded sulfur/microporous carbon sphere composite cathode material

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103811756B (en) * 2012-11-15 2018-02-27 福建省辉锐材料科技有限公司 A kind of preparation method of graphene graphite nodule composite
CN104124431B (en) * 2014-08-12 2016-11-23 长沙赛维能源科技有限公司 A kind of lithium ion battery graphite cathode material and preparation method thereof
CN104261403B (en) * 2014-10-27 2016-05-04 福州大学 A kind of preparation method of three-dimensional porous structure Graphene

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102569810A (en) * 2011-12-30 2012-07-11 常州第六元素材料科技股份有限公司 Graphene modified lithium ion battery anode material and preparation method thereof
CN102544459A (en) * 2012-01-09 2012-07-04 上海交通大学 Method for preparing graphene-coated carbon microsphere material by coating graphene oxide on carbon microsphere
CN103050666A (en) * 2012-12-12 2013-04-17 中南大学 Preparation method of silicon and carbon-coated graphene composite cathode material
CN103985873A (en) * 2014-05-19 2014-08-13 陕西科技大学 Method of improving cycling stability of negative electrode material for lithium ion battery
CN104269543A (en) * 2014-10-09 2015-01-07 南京中储新能源有限公司 Graphene-cladded sulfur/microporous carbon sphere composite cathode material

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109411723A (en) * 2018-10-16 2019-03-01 上海应用技术大学 A kind of preparation method of graphene/graphite lithium ion battery negative electrode material
CN109411723B (en) * 2018-10-16 2022-07-15 上海应用技术大学 Preparation method of graphene/graphite lithium ion battery negative electrode material
CN109585820A (en) * 2018-11-23 2019-04-05 四川大学 Si-C composite material, preparation method, application and negative electrode of lithium ion battery
CN109802115A (en) * 2019-01-15 2019-05-24 江西星盈科技有限公司 Lithium ion battery and negative electrode material and preparation method thereof
CN112803024A (en) * 2021-01-18 2021-05-14 山东玉皇新能源科技有限公司 Regeneration method and application of waste lithium ion battery negative electrode graphite material
CN113955747A (en) * 2021-10-20 2022-01-21 北京化工大学常州先进材料研究院 Preparation method of graphene-coated natural graphite negative electrode material
CN114551830A (en) * 2022-02-21 2022-05-27 海城申合科技有限公司 Preparation method of graphene oxide coated artificial graphite lithium ion negative electrode material
CN114804094A (en) * 2022-04-15 2022-07-29 广东凯金新能源科技股份有限公司 Nitrogen-graphene doped composite graphite negative electrode material and preparation method thereof
CN115000371A (en) * 2022-06-06 2022-09-02 深圳材启新材料有限公司 Preparation method of graphene-coated graphite powder

Also Published As

Publication number Publication date
CN104868106A (en) 2015-08-26

Similar Documents

Publication Publication Date Title
CN108281634A (en) A kind of method and its application of graphene coated graphite negative material of lithium ion battery
CN111326723B (en) Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof
JP6445585B2 (en) Porous carbon nanotube microspheres and production method and use thereof, metallic lithium-skeleton carbon composite material and production method thereof, negative electrode, and battery
CN105789594B (en) A kind of silicon/oxidative silicon/carbon composite and its preparation method and application
CN103633295B (en) A kind of Si-C composite material, lithium ion battery and its preparation method and application
CN104638252B (en) Silicon composited negative electrode material, preparation method of silicon composited negative electrode material and lithium ion battery
CN106848264A (en) A kind of porous silicon oxide lithium ion battery negative material and preparation method thereof
CN107342411B (en) Preparation method of graphene-silicon-carbon lithium ion battery negative electrode material
CN102983313B (en) Si-C composite material and preparation method thereof, lithium ion battery
CN107221654B (en) Three-dimensional porous nest-shaped silicon-carbon composite negative electrode material and preparation method thereof
CN104638240A (en) Method for preparing lithium ion battery silicon carbon composite anode material and product prepared by method
WO2019019410A1 (en) Modified lithium-free anode, method for preparing same, and lithium-ion battery comprising same
CN108448080A (en) A kind of graphene coated silicon/metal composite negative pole material and preparation method thereof
CN108878826B (en) Sodium manganate/graphene composite electrode material and preparation method and application thereof
CN108807915B (en) CoFe2O4Preparation method and application of/graphene composite nanofiber
CN102983317A (en) Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery
CN110415994B (en) Three-dimensional nano composite electrode material for electrochemical energy storage and preparation method thereof
CN102867945B (en) Preparation method of graphite negative electrode material containing hollow carbon nanostructure for lithium ion battery
CN111564618B (en) High-capacity lithium ion battery negative electrode material capable of being industrially produced
JP7252988B2 (en) Prelithiated negative electrode, method of making same, lithium ion battery containing prelithiated negative electrode, and supercapacitor
CN113097478A (en) Double-nanoparticle embedded nitrogen-doped porous carbon nanotube lithium ion battery cathode material and preparation method thereof
CN110085823B (en) Nano composite negative electrode material and preparation method and application thereof
CN113206249B (en) Lithium battery silicon-oxygen composite anode material with good electrochemical performance and preparation method thereof
CN108923027B (en) Organic acid modified Si/TiO2Negative electrode material of/rGO @ C lithium ion battery and preparation method and application thereof
CN110649234A (en) Preparation method of silicon-based negative electrode material with high coulombic efficiency

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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20180713