CN110190252A - A kind of lithium metal carbon composite and preparation method thereof - Google Patents
A kind of lithium metal carbon composite and preparation method thereof Download PDFInfo
- Publication number
- CN110190252A CN110190252A CN201910386497.8A CN201910386497A CN110190252A CN 110190252 A CN110190252 A CN 110190252A CN 201910386497 A CN201910386497 A CN 201910386497A CN 110190252 A CN110190252 A CN 110190252A
- Authority
- CN
- China
- Prior art keywords
- carbon
- lithium metal
- lithium
- carbon composite
- spherical
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
-
- 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
The present invention discloses a kind of lithium metal carbon composite, and spherical or spherical carrier including carbon and the lithium metal being formed in the spherical or spherical carrier hole of the carbon, the spherical or spherical carrier of carbon are reunited by the nanometer base carbon material of local graphite.The invention also discloses the preparation methods of above-mentioned lithium metal carbon composite, including are spray-dried after conductive nano carbon material, surfactant, soluble transition metal salt are dissolved in the water and obtain presoma；Presoma carbonization treatment is obtained into carbon ball；It will be washed to co-melting under an argon atmosphere with lithium metal after neutrality after carbon ball pickling, obtain metallic lithium base composite negative pole material.The lithium metal carbon composite of local graphite of the invention, in the charge and discharge process of battery, the deposition of graphited part guidance lithium metal that is orderly, being evenly distributed is more uniform, to reduce the generation of Li dendrite, increases the cycle life of lithium anode.
Description
Technical field
The present invention relates to lithium ion battery negative material more particularly to a kind of lithium metal carbon composite and its preparation sides
Method.
Background technique
Importance of the energy storage technology in today's society is more and more prominent, the clean energy resourcies such as luminous energy, wind energy, tide energy it is big
The fields such as scale storage, large scale electric network peak regulation, communications and transportation, portable equipment, job that requires special skills increasingly be unable to do without energy storage technology
Application.Wherein, lithium-ion battery system is because of energy density with higher, longer cycle life, the design of flexible structure
The advantages that and large-scale application in communications and transportation and portable equipment.Traditional is anode with LiFePO4, ternary material etc., with
Graphite type material has been approached theoretical limit, the promotion speed of energy density as the lithium-ion battery system mass energy density of cathode
Degree can not adapt to the growth of social demand.Clearly the year two thousand twenty is arrived in proposition in " made in China 2025 " white paper for country, I
State's power battery will reach energy density 300wh/kg, reach 400wh/kg within 2025, the year two thousand thirty reaches 500wh/kg.To improve
Energy mass energy density, it is necessary to the architecture of revolutionary change battery.It is negative in lithium ion battery with metallic lithium base material
Pole can not only give full play to the capacity containing lithium anode material, can also use the high capacity anode without lithium, as sulphur, sulphur carbon are multiple
The materials such as conjunction.Also, metallic lithium base material cathode can be with substantially reduced cathode quality, to improve the total quality energy of battery
Density.
However directly used in lithium-ion battery system in the prior art lithium metal as cathode can because lithium metal from
The random deposition of son generates Li dendrite, greatly shortens the cycle life of lithium anode, reduces the security performance of battery.
Also have in the prior art and obtains lithium metal after preparing a kind of skeleton carbon ball and lithium metal melting using spray drying process
Carbon compound cathode materials, but since it is controlled and guided to being deposited without for lithium metal, so that the deposition of lithium is unordered, lithium
It is distributed not uniform enough.
Summary of the invention
The lithium metal carbon composite and its system that the object of the present invention is to provide a kind of lithium metals orderly to deposit, is evenly distributed
Preparation Method.
Technical scheme is as follows:
The present invention provides a kind of lithium metal carbon composite, spherical or spherical carrier including carbon and is formed in described
The spherical or spherical carrier of lithium metal in the spherical or spherical carrier hole of carbon, the carbon is reunited by nanometer base carbon material
It forms, the nanometer base carbon material local graphite.
The present invention also provides a kind of preparation methods of lithium metal carbon composite, comprising the following steps:
Step 1: conductive nano carbon material, high molecular surfactant, soluble transition metal salt are dissolved in the water,
Then spray drying obtains presoma；
Step 2: the presoma carbonization treatment is obtained into carbon ball；
Step 3: neutrality will be washed to after the carbon ball pickling；
Step 4: the carbon ball is co-melting under an argon atmosphere with lithium metal, obtain metallic lithium base composite negative pole material.
In the present invention, transition metal soluble salt is dissolved in uniformly to add after water and forms presoma in nano-carbon material,
For the presoma in carbonization treatment, transition metal salt is reduced into transition metal simple substance by carbon, and the transition metal simple substance is into one
When step continues carbonization, as the catalyst of carbon graphite, to make nanometer base carbon material in the position graphite with transition metal
Change.It due to orderly in nano-carbon material of soluble transition metal salt and is uniformly distributed, so that graphited position is distributed
It is relatively orderly and uniform.
In the charge and discharge process of battery, since the intercalation potential of graphitized carbon is higher than lithium metal, so lithium metal is first
It is deposited on the surface for the graphitized carbon being evenly distributed, to effectively guide lithium metal deposition more uniform, reduces lithium branch
Brilliant generation.
Preferably, the carbonization treatment is to be heated to 500-1000 DEG C in nitrogen atmosphere and keep the temperature 1-12h；More preferably
The carbonization treatment is to be heated to 800 DEG C in nitrogen atmosphere and keep the temperature 6h.
Preferably, the conductive nano carbon material is carbon nanotube, carbon nano-fiber, graphene or Ketjen black.
Preferably, the high molecular surfactant be polyvinylpyrrolidone, cationic starch, carboxymethyl cellulose or
Hydroxypropyl cellulose.
Preferably, the water-soluble transition metal salt is molysite, cobalt salt or nickel salt.Further, the molysite is nitre
Sour iron or ferric sulfate；The cobalt salt is cobalt chloride or cobaltous sulfate；The nickel salt is nickel nitrate, nickel sulfate or nickel acetate.
Preferably, the intake air temperature of the spray drying is 105 DEG C -300 DEG C, admission pressure 0.2MPa-0.6MPa, into
Material speed is 3-15ml/min.
Beneficial effects of the present invention:
The carbon ball shape of lithium metal carbon composite of the invention or spherical carrier are by nanometer sill reunion face at described
Nanometer base carbon material local graphite and have good electric conductivity, pore structure abundant, higher specific surface area.In battery
In charge and discharge process, graphitization part guidance lithium metal deposition that is orderly, being evenly distributed is more uniform, to reduce Li dendrite
Generation, increase the cycle life of lithium anode, while pore structure abundant and three-dimensional conductive network improve lithium metal
Utilization rate, to improve the energy density of battery.
Detailed description of the invention
Fig. 1 is the transmission electron microscope figure of lithium metal carbon composite prepared by the present invention.
Specific embodiment
It elaborates below with reference to embodiment to the present invention.It should be noted that for these embodiments
Illustrate to be used to help understand the present invention, but and does not constitute a limitation of the invention.
Embodiment 1
By 70g cationic starch and 30g Ni (CH3COO)2·4H2O is dissolved in 500ml deionized water, with stirring to complete
Fully dissolved obtains green solution.30g Ketjen black is added with the revolving speed mechanical stirring 12h of 500rpm, is during which dispersed using ultrasonic wave
Instrument disperses 6h, obtains evenly dispersed black paste.Black paste is spray-dried, 105 DEG C of spraying intake air temperature,
Admission pressure 0.2MPa, feed rate 3ml/min, obtains precursor powder.
Above-mentioned precursor powder is placed in tube furnace, nitrogen atmosphere is passed through, is heated to 1000 DEG C of heat preservation 1h, is had
The local graphite carbon ball of nano-micro structure.In this carbonisation, cationic starch becomes amorphous carbon, Ni in carbonization2+
Elemental nickel is reduced by carbon, nickel simple substance is used as the graphited catalyst of amorphous carbon in the carbonisation continued to, from
And it is graphitized the amorphous carbon after carbonization at the position with metal simple-substance nickel.Due to cationic starch and solubility Ni
(CH3COO)2·4H2O has been dissolved into water, then be joined nano-carbon material Ketjen black and is uniformly dispersed, so that Ni
(CH3COO)2In Ni2+It is formed in cationic starch and orderly and is uniformly distributed, and then become nothing in cationic starch carbonization
It orderly and is uniformly distributed after setting carbon, so that the distribution of amorphous carbon graphited position is also relatively orderly and uniformly.
Above-mentioned carbon ball is dispersed in the HNO of 2M3In, 120 DEG C be heated at reflux 12h carry out pickling, then filter and spend from
After sub- water cleaning carbon ball to neutrality, vacuum drying is for 24 hours.In the process, since metallic nickel simple substance is corroded in acid cleaning process
Fall, pore structure uniform and abundant is further formd on carbon composite, makes carbon composite specific surface with higher
Product；Meanwhile carbon-carbon composite material surface introduces oxy functional groups in acid cleaning process, to increase carbon composite and melting
Wellability between state lithium metal allows molten metal lithium by porous C-base composte material uniform pickup.
By in the above-mentioned carbon ball of 4g and the reaction kettle of 6g lithium metal merging argon gas protection, 200 DEG C are warming up to, 20min, system are kept the temperature
Obtaining material is lithium metal carbon compound cathode materials.
Fig. 1 is the transmission electron microscope figure of lithium metal carbon composite obtained by the present embodiment, used micro- in figure
Mirror is JEM-2100, and test acceleration voltage is 200KV, discharge-rate 8000.It can be taken a fancy to by Fig. 1, the institute in white edge in figure
Show that there is the shade of the nanometer base carbon material local graphite in lithium carbon composite in part.From this figure, it can be seen that lithium carbon is compound
Nanometer base carbon material graphitization position in material is evenly distributed orderly.
Electric performance test:
Above-mentioned made lithium metal carbon composite is prepared into soft-package battery, cell body as lithium ion battery negative material
Be as follows: anode constituents are the LiFePO4, Kynoar, Super P, carbon nanotube that mass ratio is 90:2:4:4, anode
Active material surface density is 10mg/cm2；Electrolyte lithium salts is the LiPF of 1M6, solvent be volume ratio be 1:1 ethylene carbonate and
Dimethyl carbonate.Battery carries out 0.1C charge and discharge, recycles 100 times, and battery capacity conservation rate is 89%.
Embodiment 2
By 50g carboxymethyl cellulose and 20g Fe (NO3)3·9H2O is dissolved in 700ml deionized water, and magnetic agitation is extremely
It is completely dissolved, obtains yellow clear transparent solutions.It is added after 50g Ketjen black with the revolving speed mechanical stirring 12h of 500rpm, during which makes
Disperse 6h with ultrasonic wave separating apparatus, obtains evenly dispersed black paste.Black paste is spray-dried, air inlet is set
200 DEG C of temperature, admission pressure 0.6MPa, feed rate 15ml/min obtain precursor powder.
Above-mentioned precursor powder is placed in tube furnace, nitrogen atmosphere is passed through, is heated to 800 DEG C of heat preservation 6h, is had
The local graphite carbon ball of nano-micro structure.In this carbonisation, carboxymethyl cellulose becomes amorphous carbon in carbonization,
Fe3+Fe is reduced by carbon, iron simple substance is used as the graphited catalyst of amorphous carbon in the carbonisation continued to,
To make the amorphous carbon after carbonization be graphitized at the position with metal simple-substance iron.Due to carboxymethyl cellulose and Fe
(NO3)3·9H2O has been dissolved into water, then be joined Ketjen black and is uniformly dispersed, so that Fe (NO3)3In Fe3+In carboxylic first
It is formed in base cellulose orderly and uniform distribution, and then orderly uniform after carboxymethyl cellulose carbonization becomes amorphous carbon
Distribution, so that the graphited position distribution of amorphous carbon is also relatively orderly and uniform.
Above-mentioned carbon ball is dispersed in the HNO of 2M3In, 120 DEG C be heated at reflux 12h carry out pickling, then filter and spend from
After sub- water cleaning carbon ball to neutrality, vacuum drying is for 24 hours.In the process, since metallic iron simple substance is corroded in acid cleaning process
Fall, pore structure uniform and abundant is further formd on carbon composite, makes carbon composite specific surface with higher
Product；Meanwhile carbon-carbon composite material surface introduces oxy functional groups in acid cleaning process, to increase carbon composite and melting
Wellability between state lithium metal allows molten metal lithium by porous C-base composte material uniform pickup.
By in the above-mentioned carbon ball of 5g and the reaction kettle of 5g lithium metal merging argon gas protection, 200 DEG C are warming up to, 20min is kept the temperature.Institute
Obtaining material is lithium metal carbon compound cathode materials.
Using with the identical battery system of embodiment 1 and test method, carry out charge and discharge cycles 100 times, battery capacity protect
Holdup is 95.3%.
Embodiment 3
By 30g hydroxypropyl cellulose and 15g CoSO4·7H2O is dissolved in 800ml deionized water, and magnetic agitation is to complete
Dissolution, obtains red clear transparent solutions.70g carbon nano-fiber is added with the revolving speed mechanical stirring 12h of 500rpm, during which uses
Ultrasonic wave separating apparatus disperses 6h, obtains evenly dispersed black paste.Black paste is spray-dried, air inlet temperature is set
300 DEG C, admission pressure 0.4MPa, feed rate 9ml/min of degree obtains precursor powder.
Precursor powder is placed in tube furnace, nitrogen atmosphere is passed through, is heated to 500 DEG C of heat preservation 12h, is obtained micro- with receiving
The local graphite carbon ball of structure.In this carbonisation, hydroxypropyl cellulose becomes amorphous carbon, Co when being carbonized2+By carbon
It is reduced into simple substance cobalt, cobalt simple substance is used as the graphited catalyst of amorphous carbon in the carbonisation continued to, to make
Amorphous carbon after carbonization is graphitized at the position with metal list cobalt.Due to hydroxypropyl cellulose and solubility CoSO4·7H2O
It has been dissolved into water, then joined carbon nano-fiber and be uniformly dispersed, so that CoSO4In Co2+In hydroxypropyl cellulose
It is formed and orderly and is uniformly distributed, and then had after hydroxypropyl cellulose carbonization becomes amorphous carbon and fill and be uniformly distributed, in this way
So that the graphited position distribution of amorphous carbon is also relatively orderly and uniform.
Above-mentioned carbon ball is dispersed in the HNO of 2M3In, 120 DEG C be heated at reflux 12h carry out pickling, then filter and spend from
After sub- water cleaning carbon ball to neutrality, vacuum drying is for 24 hours.In the process, since metallic cobalt simple substance is corroded in acid cleaning process
Fall, pore structure uniform and abundant is further formd on carbon composite, makes carbon composite specific surface with higher
Product；Meanwhile carbon-carbon composite material surface introduces oxy functional groups in acid cleaning process, to increase carbon composite and melting
Wellability between state lithium metal allows molten metal lithium by porous C-base composte material uniform pickup.
By in the above-mentioned carbon ball of 3g and the reaction kettle of 7g lithium metal merging argon gas protection, 200 DEG C are warming up to, 20min is kept the temperature.Institute
Obtaining material is lithium metal carbon compound cathode materials.
Using with the identical battery system of embodiment 1 and test method, carry out charge and discharge cycles 100 times, battery capacity protect
Holdup is 92.6%.
Embodiment 4:
By 10g polyvinylpyrrolidone and 6g Ni (NO3)2·6H2O is dissolved in 1000ml deionized water, magnetic agitation
To being completely dissolved, green clear transparent solutions are obtained.90g graphene is added with the revolving speed mechanical stirring 12h of 500rpm, during which makes
Disperse 6h with ultrasonic wave separating apparatus, obtains evenly dispersed black paste.Black paste is spray-dried, air inlet is set
200 DEG C of temperature, admission pressure 0.4MPa, feed rate 6ml/min obtain precursor powder.
Precursor powder is placed in tube furnace, nitrogen atmosphere is passed through, is heated to 800 DEG C of heat preservation 2h, is obtained micro- with receiving
The local graphite carbon ball of structure.In this carbonisation, polyvinylpyrrolidone becomes amorphous carbon, Ni in carbonization2+
Elemental nickel is reduced by carbon, nickel simple substance is in the carbonisation continued to, as the graphited catalyst of amorphous carbon, from
And it is graphitized the amorphous carbon after carbonization at the position with metal simple-substance nickel.Due to polyvinylpyrrolidone and solubility Ni
(NO3)2·6H2O has been dissolved into water, and it is uniform then to joined nano-carbon material graphene dispersion, so that Ni (NO3)2In
Ni2+It is formed in polyvinylpyrrolidone and orderly and is uniformly distributed, and then become amorphous in polyvinylpyrrolidone carbonization
It orderly and is uniformly distributed after carbon, so that the distribution of amorphous carbon graphited position is also relatively orderly and uniformly.
Above-mentioned carbon ball is dispersed in the HNO of 2M3In, 120 DEG C are heated at reflux 12h pickling, then filter and use deionized water
After cleaning carbon ball to neutrality, vacuum drying is for 24 hours.In the process, since metallic nickel simple substance is corroded in acid cleaning process, into
One step forms pore structure uniform and abundant on carbon composite, makes carbon composite specific surface area with higher；Together
When, carbon-carbon composite material surface introduces oxy functional groups in acid cleaning process, to increase carbon composite and molten state gold
Belong to the wellability between lithium, allows molten metal lithium by porous C-base composte material uniform pickup.
By in the above-mentioned carbon ball of 8g and the reaction kettle of 2g lithium metal merging argon gas protection, 200 DEG C of set temperature, 20min is kept the temperature.
Resulting materials are lithium metal carbon compound cathode materials.
Using with the identical battery system of embodiment 1 and test method, carry out charge and discharge cycles 100 times, battery capacity protect
Holdup is 91.8%.
Embodiment 5:
By 50g polyvinylpyrrolidone and 5g FeSO4·7H2O is dissolved in 1000ml deionized water, and magnetic agitation is to complete
Fully dissolved obtains green solution.50g carbon nanotube is added with the revolving speed mechanical stirring 12h of 500rpm, during which using ultrasonic wavelength-division
It dissipates instrument and disperses 6h, obtain evenly dispersed black paste.Black paste is spray-dried, sets 200 DEG C of intake air temperature,
Admission pressure 0.4MPa, feed rate 6ml/min, obtains precursor powder.
Above-mentioned precursor powder is placed in tube furnace, nitrogen atmosphere is passed through, is heated to 800 DEG C of heat preservation 2h, is had
The local graphite carbon ball of nano-micro structure.In this carbonisation, polyvinylpyrrolidone becomes amorphous carbon in carbonization,
Fe2+Fe is reduced by carbon, iron simple substance is used as the graphited catalyst of amorphous carbon in the carbonisation continued to,
To make the amorphous carbon after carbonization be graphitized at the position with metal simple-substance iron.Due to polyvinylpyrrolidone and solubility
FeSO4·7H2O has been dissolved into water, then be joined carbon nanotube and is uniformly dispersed, so that FeSO4In Fe2+In polyethylene
It is formed in pyrrolidones and orderly and is uniformly distributed, and then is orderly and equal after polyvinylpyrrolidone carbonization becomes amorphous carbon
Even distribution, so that the graphited position distribution of amorphous carbon is also relatively orderly and uniform.
Above-mentioned carbon ball is dispersed in the HNO of 2M3In, 120 DEG C are heated at reflux 12h pickling, filter and are cleaned with deionized water
After carbon ball to neutrality, vacuum drying is for 24 hours.In the process, since metallic iron simple substance is corroded in acid cleaning process, further
Pore structure uniform and abundant is formd on carbon composite, makes carbon composite specific surface area with higher；Meanwhile
Carbon-carbon composite material surface introduces oxy functional groups in acid cleaning process, thus increase carbon composite and molten metal lithium it
Between wellability, allow molten metal lithium by porous C-base composte material uniform pickup.
By in the above-mentioned carbon ball of 8g and the reaction kettle of 2g lithium metal merging argon gas protection, 200 DEG C are warming up to, 20min is kept the temperature.Institute
Obtaining material is lithium metal carbon compound cathode materials.
Using with the identical battery system of embodiment 1 and test method, carry out charge and discharge cycles 100 times, battery capacity protect
Holdup is 86.4%.
Embodiment 6:
By 30g polyvinylpyrrolidone and 10g CoCl2·6H2O is dissolved in 1000ml deionized water, and magnetic agitation is extremely
It is completely dissolved, obtains red solution.70g carbon nanotube is added with the revolving speed mechanical stirring 12h of 500rpm, during which uses ultrasonic wave
Separating apparatus disperses 6h, obtains evenly dispersed black paste.Black paste is spray-dried, intake air temperature 200 is set
DEG C, admission pressure 0.4MPa, feed rate 6ml/min obtain precursor powder.
Above-mentioned precursor powder is placed in tube furnace, nitrogen atmosphere is passed through, is heated to 800 DEG C of heat preservation 2h, is had
The local graphite carbon ball of nano-micro structure.In this carbonisation, polyvinylpyrrolidone becomes amorphous carbon when being carbonized,
Co2+Simple substance cobalt is reduced by carbon, cobalt simple substance in the carbonisation continued to as the catalyst of carbon graphite, to make
Amorphous carbon after carbonization is graphitized at the position with metal simple substance cobalt.Due to polyvinylpyrrolidone and solubility
CoCl2·6H2O has been dissolved into water, then be joined carbon nanotube and is uniformly dispersed, so that CoCl2In Co2+In polyethylene
It is formed in pyrrolidones and orderly and is uniformly distributed, and then is orderly and equal after polyvinylpyrrolidone carbonization becomes amorphous carbon
Even distribution, so that the graphited position distribution of amorphous carbon is also relatively orderly and uniform, so that graphited position
Distribution is also relatively orderly and uniform.
Above-mentioned carbon ball is dispersed in the HNO of 2M3In, 120 DEG C are heated at reflux 12h pickling, filter and are cleaned with deionized water
After carbon ball to neutrality, vacuum drying is for 24 hours.In the process, since metallic cobalt simple substance is corroded in acid cleaning process, further
Pore structure uniform and abundant is formd on carbon composite, makes carbon composite specific surface area with higher；Meanwhile
Carbon-carbon composite material surface introduces oxy functional groups in acid cleaning process, thus increase carbon composite and molten metal lithium it
Between wellability, allow molten metal lithium by porous C-base composte material uniform pickup.
By in the above-mentioned carbon ball of 8g and the reaction kettle of 2g lithium metal merging argon gas protection, 200 DEG C of set temperature, 20min is kept the temperature.
Resulting materials are lithium metal carbon compound cathode materials.
Using with the identical battery system of embodiment 1 and test method, carry out charge and discharge cycles 100 times, battery capacity protect
Holdup is 90.3%.
Embodiment 7:
By 50g polyvinylpyrrolidone and 30g NiSO4·6H2O is dissolved in 1000ml deionized water, and magnetic agitation is extremely
It is completely dissolved, obtains green solution.50g carbon nanotube is added with the revolving speed mechanical stirring 12h of 500rpm, during which uses ultrasonic wave
Separating apparatus disperses 6h, obtains evenly dispersed black paste.Black paste is spray-dried, intake air temperature 200 is set
DEG C, admission pressure 0.4MPa, feed rate 6ml/min obtain precursor powder.
Precursor powder is placed in tube furnace, nitrogen atmosphere is passed through, is heated to 800 DEG C of heat preservation 2h, is obtained micro- with receiving
The local graphite carbon ball of structure.In this carbonisation, polyvinylpyrrolidone becomes amorphous carbon, Ni in carbonization2+
Elemental nickel is reduced by carbon, nickel simple substance in the carbonisation continued to as the catalyst of carbon graphite, to make carbon
Amorphous carbon after change is graphitized at the position with metal simple-substance nickel.Due to polyvinylpyrrolidone and solubility NiSO4·
6H2O has been dissolved into water, then be joined carbon nanotube and is uniformly dispersed, so that NiSO4In Ni2+In polyvinylpyrrolidine
Orderly and uniformly distribution is formed in ketone, and then orderly and uniform point after polyvinylpyrrolidone carbonization becomes amorphous carbon
Cloth, so that the graphited position distribution of amorphous carbon is also relatively orderly and uniform.
Above-mentioned carbon ball is dispersed in the HNO of 2M3In, 120 DEG C are heated at reflux 12h pickling, then filter and use deionized water
After cleaning carbon ball to neutrality, vacuum drying is for 24 hours.In the process, since metallic nickel simple substance is corroded in acid cleaning process, into
One step forms pore structure uniform and abundant on carbon composite, makes carbon composite specific surface area with higher；Together
When, carbon-carbon composite material surface introduces oxy functional groups in acid cleaning process, to increase carbon composite and molten state gold
Belong to the wellability between lithium, allows molten metal lithium by porous C-base composte material uniform pickup.
By in the above-mentioned carbon ball of 8g and the reaction kettle of 2g lithium metal merging argon gas protection, 200 DEG C of set temperature, 20min is kept the temperature.
Resulting materials are lithium metal carbon compound cathode materials.
Using with the identical battery system of embodiment 1 and test method, carry out charge and discharge cycles 100 times, battery capacity protect
Holdup is 93.7%.
In the present invention, transition metal soluble salt is uniformly added and forms presoma in nano-carbon material, the forerunner
For body in carbonization treatment, transition metal salt is reduced into transition metal simple substance by carbon, which is continuing to carbon
When change, as the graphited catalyst of amorphous carbon, so that nanometer base carbon material be made to be graphitized at the position with transition metal.
It due to orderly in nano-carbon material of soluble transition metal salt and is uniformly distributed, so that the distribution of graphited position is also opposite
Orderly and uniformly.
Since transition metal simple substance is corroded in the postorder acid cleaning process of acid, further formed on carbon composite
Uniform and abundant pore structure, specific surface area with higher；Meanwhile carbon-carbon composite material surface introduces in acid cleaning process
Oxy functional groups, to increase the wellability between carbon composite and molten metal lithium.So that molten metal lithium can
By porous C-base composte material uniform pickup.
In the carbon ball shape of lithium metal carbon composite of the invention or spherical carrier by nanometer sill reunion face at institute
It states nanometer base carbon material local graphite and there is good electric conductivity, pore structure abundant, higher specific surface area.In battery
Charge and discharge process in, the deposition of graphited part guidance lithium metal so that deposition lithium it is more uniform, to reduce lithium branch
Brilliant generation, increases the cycle life of lithium anode, while pore structure abundant and three-dimensional conductive network improve lithium metal
Utilization rate, to improve the energy density of battery.
It also may be adapted to the cell bodies such as liquid or solid-state, gel state using the lithium metal carbon composite that the present invention makes
System.Certainly it can be applied to the battery system of similar system after lithium metal being replaced, such as: potassium battery, sode cell etc..This method
Simple process is applicable to be mass produced.There is energy density height, circulation longevity with liquid prepared by the present invention, solid state battery
Order long feature.
It should be noted that being used to help understand the present invention for the explanation of these embodiments, but do not constitute
Limitation of the invention.In addition, as long as technical characteristic of the present invention described in each embodiment does not constitute punching each other
It is prominent to be combined with each other.In addition the above is only section Example of the invention, rather than whole embodiments, based in the present invention
Embodiment, those of ordinary skill in the art's every other implementation obtained without making creative work
Example, shall fall within the protection scope of the present invention.
Claims (9)
1. a kind of lithium metal carbon composite, spherical or spherical carrier including carbon and the spherical shape or class for being formed in the carbon
Lithium metal in ball type carrier hole, which is characterized in that the spherical or spherical carrier of the carbon is reunited by nanometer base carbon material
It forms, the nanometer base carbon material local graphite.
2. the preparation method of lithium metal carbon composite as described in claim 1, comprising the following steps:
Step 1: conductive nano carbon material, high molecular surfactant, soluble transition metal salt are dissolved in the water, then
Spray drying obtains presoma；
Step 2: the presoma carbonization treatment is obtained into carbon ball；
Step 3: neutrality will be washed to after the carbon ball pickling；
Step 4: the carbon ball is co-melting under an argon atmosphere with lithium metal, obtain metallic lithium base composite negative pole material.
3. the preparation method of lithium metal carbon composite as claimed in claim 2, which is characterized in that the carbonization treatment be
It is heated to 500-1000 DEG C in nitrogen atmosphere and keeps the temperature 1-12h.
4. the preparation method of lithium metal carbon composite as claimed in claim 2, which is characterized in that the carbonization treatment be
It is heated to 800 DEG C in nitrogen atmosphere and keeps the temperature 6h.
5. the preparation method of lithium metal carbon composite as claimed in claim 2, which is characterized in that the conductive nano carbon materials
Material is carbon nanotube, carbon nano-fiber, graphene or Ketjen black.
6. the preparation method of the lithium metal carbon composite as described in claim 2 or 5, which is characterized in that the high molecular form
Face activating agent is polyvinylpyrrolidone, cationic starch, carboxymethyl cellulose or hydroxypropyl cellulose.
7. the preparation method of the lithium metal carbon composite as described in claim 2 or 5, which is characterized in that the solubility
Transition metal salt is molysite, cobalt salt or nickel salt.
8. the preparation method of lithium metal carbon composite as claimed in claim 7, which is characterized in that the molysite is ferric nitrate
Or ferrous sulfate；The cobalt salt is cobalt chloride or cobaltous sulfate；The nickel salt is nickel nitrate, nickel sulfate or nickel acetate.
9. the preparation method of the lithium metal carbon composite as described in right asks 2, which is characterized in that the air inlet of the spray drying
Mouth temperature is 105 DEG C -300 DEG C, admission pressure 0.2MPa-0.6MPa, charging rate 3-15ml/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910386497.8A CN110190252B (en) | 2019-05-09 | 2019-05-09 | Metal lithium-carbon composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910386497.8A CN110190252B (en) | 2019-05-09 | 2019-05-09 | Metal lithium-carbon composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110190252A true CN110190252A (en) | 2019-08-30 |
| CN110190252B CN110190252B (en) | 2022-04-01 |
Family
ID=67714425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910386497.8A Active CN110190252B (en) | 2019-05-09 | 2019-05-09 | Metal lithium-carbon composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110190252B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112820857A (en) * | 2019-11-15 | 2021-05-18 | 中国科学院成都有机化学有限公司 | Nano carbon composite lithium metal cathode and preparation method thereof |
| CN114188509A (en) * | 2021-12-01 | 2022-03-15 | 杭州电子科技大学 | Preparation method of lithium sulfide electrode based on carbon nanotube packaging means |
| WO2023030092A1 (en) * | 2021-09-02 | 2023-03-09 | 天津中能锂业有限公司 | Complex formed by network skeleton material having lithiophilic modification layer and metal lithium, and preparation method therefor and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1207572A1 (en) * | 2000-11-15 | 2002-05-22 | Dr. Sugnaux Consulting | Mesoporous electrodes for electrochemical cells and their production method |
| US20080274406A1 (en) * | 2004-06-30 | 2008-11-06 | Mitsubishi Chemical Corporation | Negative Electrode Material for Lithium Secondary Battery, Method for Producing Same, Negative Electrode for Lithium Secondary Battery Using Same and Lithium Secondary Battery |
| CN102751500A (en) * | 2012-07-17 | 2012-10-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Amorphous carbon material with graphitizing characteristics and preparation method of amorphous carbon material |
| CN105374991A (en) * | 2014-08-13 | 2016-03-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal lithium-framework carbon composite material and preparation method thereof, negative electrode and secondary battery |
| CN109467080A (en) * | 2018-08-13 | 2019-03-15 | 国网浙江省电力有限公司湖州供电公司 | A kind of graphitization hollow carbon method for preparing microsphere can be used for carrying sulphur and its application |
-
2019
- 2019-05-09 CN CN201910386497.8A patent/CN110190252B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1207572A1 (en) * | 2000-11-15 | 2002-05-22 | Dr. Sugnaux Consulting | Mesoporous electrodes for electrochemical cells and their production method |
| US20080274406A1 (en) * | 2004-06-30 | 2008-11-06 | Mitsubishi Chemical Corporation | Negative Electrode Material for Lithium Secondary Battery, Method for Producing Same, Negative Electrode for Lithium Secondary Battery Using Same and Lithium Secondary Battery |
| CN102751500A (en) * | 2012-07-17 | 2012-10-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Amorphous carbon material with graphitizing characteristics and preparation method of amorphous carbon material |
| CN105374991A (en) * | 2014-08-13 | 2016-03-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal lithium-framework carbon composite material and preparation method thereof, negative electrode and secondary battery |
| CN109467080A (en) * | 2018-08-13 | 2019-03-15 | 国网浙江省电力有限公司湖州供电公司 | A kind of graphitization hollow carbon method for preparing microsphere can be used for carrying sulphur and its application |
Non-Patent Citations (1)
| Title |
|---|
| TONG-TONG ZUO ET AL: "Graphitized Carbon Fibers as Multifunctional 3D Current Collectors for High Areal Capacity Li Anodes", 《ADVANCED MATERIALS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112820857A (en) * | 2019-11-15 | 2021-05-18 | 中国科学院成都有机化学有限公司 | Nano carbon composite lithium metal cathode and preparation method thereof |
| WO2023030092A1 (en) * | 2021-09-02 | 2023-03-09 | 天津中能锂业有限公司 | Complex formed by network skeleton material having lithiophilic modification layer and metal lithium, and preparation method therefor and application thereof |
| CN114188509A (en) * | 2021-12-01 | 2022-03-15 | 杭州电子科技大学 | Preparation method of lithium sulfide electrode based on carbon nanotube packaging means |
| CN114188509B (en) * | 2021-12-01 | 2023-12-01 | 杭州电子科技大学 | Preparation method of lithium sulfide electrode based on carbon nano tube packaging means |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110190252B (en) | 2022-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105895886B (en) | A kind of sodium-ion battery transition metal phosphide/porous anode composite and preparation method thereof | |
| JP6334231B2 (en) | Graphite negative electrode material for lithium ion battery and method for producing the same | |
| CN108550821B (en) | Preparation method of core-shell structure nickel phosphide/carbon microspheres based on Ni-MOF | |
| CN108878849A (en) | The synthesis technology of rich oxidate for lithium and lithium ion battery containing the richness oxidate for lithium | |
| CN108574089B (en) | Preparation method of hollow tubular lithium-rich manganese-based positive electrode material | |
| CN109860593B (en) | Iron-nickel sulfide, preparation method thereof and sodium ion battery using iron-nickel sulfide as negative electrode | |
| CN110190252A (en) | A kind of lithium metal carbon composite and preparation method thereof | |
| CN109713261A (en) | Carbonization silk fabric/transition metal oxide composite material and preparation method for flexible lithium ion battery cathode | |
| CN110518213A (en) | A kind of porous silicon-carbon nano tube compound material and its preparation method and application | |
| CN111146424B (en) | Metal sulfide/carbon composite material, and preparation method and application thereof | |
| CN113054183A (en) | Preparation method of CoNi bimetal organic framework derived carbon-sulfur composite material | |
| CN108807915B (en) | CoFe2O4Preparation method and application of/graphene composite nanofiber | |
| CN107464938B (en) | Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery | |
| CN111370663B (en) | Porous silicon @ amorphous carbon/carbon nanotube composite material and preparation method and application thereof | |
| CN109449390A (en) | A kind of iron oxide/graphene aerogel composite negative pole material and preparation method thereof | |
| CN114275777A (en) | Preparation method of high-graphitization-degree carbon-based material for lithium battery negative electrode | |
| CN110416501B (en) | Electrostatic self-assembly three-dimensional flower-shaped cobalt disulfide/rGO composite material and preparation method and application thereof | |
| CN103400980A (en) | Iron sesquioxide/nickel oxide core-shell nanorod array film as well as preparation method and application thereof | |
| CN111211312A (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN102437334B (en) | Microwave hydrothermal synthesizing method for carbon nanotube/LiFePO4 lithium ion battery anode material | |
| CN111952577B (en) | C/Si/CNTs composite carbon nanofiber membrane, preparation method and application thereof | |
| CN110148745B (en) | Hollow spherical ferrous sulfide nano material and preparation method and application thereof | |
| CN110171828B (en) | FeS nano material based on carbon cloth directional growth and preparation method and application thereof | |
| CN110474023B (en) | Fibrous nickel-bismuth battery and preparation method thereof | |
| CN107732206B (en) | Preparation method of bimetallic oxide composite negative electrode material with multilevel structure |
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 |