CN110061199A - A kind of composite negative pole material of metal-carbon and its preparation method and application - Google Patents
A kind of composite negative pole material of metal-carbon and its preparation method and application Download PDFInfo
- Publication number
- CN110061199A CN110061199A CN201810057247.5A CN201810057247A CN110061199A CN 110061199 A CN110061199 A CN 110061199A CN 201810057247 A CN201810057247 A CN 201810057247A CN 110061199 A CN110061199 A CN 110061199A
- Authority
- CN
- China
- Prior art keywords
- metal
- coal
- sintering
- negative pole
- carbon
- 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
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to battery material fields, and in particular to bituminous coal is mixed to obtain mixture with source metal by a kind of preparation method of the composite negative pole material of metal-carbon；Mixture is successively through one-stage sintering, bis sintering and three-stage sintering；Obtain the composite negative pole material；Wherein, the temperature of one-stage sintering is for 300 DEG C and following；The temperature of bis sintering is 400~600 DEG C；The temperature of three-stage sintering is 700~1200 DEG C.The invention also includes preparing the application in negative electrode of lithium ion battery using negative electrode material made from the preparation method, and by the negative electrode material.The present invention originally uses bituminous coal as raw material；The raw material and source metal are cooperated, and under the distinctive three-stage sintering mechanism, the cell negative electrode material with excellent electric property can be made.
Description
Technical field
The present invention relates to a kind of cathode material for high capacity lithium ion battery and preparation method thereof, belong to cell negative electrode material neck
Domain.
Background technique
Lithium ion battery energy density, cycle life, the scope of application and in terms of have many advantages, such as, be
The energy conversion of great development prospect and memory device at this stage.Negative electrode material be influence its comprehensive performance key factor it
One, obtain extensive and in-depth research.Have been reported that the type that can be used as lithium ion battery negative material mainly includes carbon at present
Material, alloy material and metal oxide materials.Wherein, graphite-like carbon is main commercialization negative electrode material, and performance is stablized
But specific capacity is lower；Alloy material of cathode and oxide cathode material all have the advantages that theoretical capacity is high and has a safety feature,
It is very potential novel anode material, but the deintercalation repeatedly of lithium ion can cause the volume expansion and contraction of material, cause
Material fragmentation and dusting cause the problems such as capacitance loss for the first time of battery is big, cyclical stability is poor, multiplying power discharging property is poor.
In order to solve these problems present in alloy or metal oxide negative electrode material, existing technical solution is usually
Using conductive carbon as cushioning frame, carbon and alloy or metal oxide are combined, effectively buffer its existing volume expansion simultaneously
Electrode conductivuty is improved, the structural stability in charge and discharge process is improved.In addition, by material nano or filming or preparation three
Dimension porous material can also solve the problems, such as that cycle performance caused by its volume expansion is bad to a certain extent.
Carbon nano-fiber is dispersed in cobalt salt solution by patent CN10122344A, is added aqueous slkali and is obtained carbon Nanowire
Dimension-cobalt hydroxide compound, this compound produce the composite negative pole material containing cobalt/cobalt oxide after being heat-treated under certain atmosphere.
Patent CN104051718A mixes the aqueous chloride solution of tin with transition metal cyanide compound aqueous solution, by collosol and gel and cold
Freeze drying process and form tinbase cyanogen colloid system, and be heat-treated under air or oxygen atmosphere as presoma, obtains one
The three-D nano-porous stannic oxide base composite oxidate of kind.Although to alloy type or metal oxide-type in current document or patent
The modification of negative electrode material can effectively alleviate the problem of poorly conductive and volume expansion, improved battery electricity mostly
Chemical property, but there is also used preparation processes it is complicated, raw material are expensive, high production cost the problems such as, be unsuitable for reality
Production and application.
Summary of the invention
An object of the present disclosure is, provides a kind of preparation method of the composite negative pole material of metal-carbon.
It is a second object of the invention to provide a kind of composite negative pole of metal-carbon made from preparation method
Material.
It is a third object of the invention to provide the application of the composite negative pole material.
A kind of preparation method of the composite negative pole material of metal-carbon, mixes to obtain mixture with source metal for bituminous coal；Mixture
Successively through one-stage sintering, bis sintering and three-stage sintering；Obtain the composite negative pole material；Wherein, the temperature of one-stage sintering
It is for 300 DEG C and following；The temperature of bis sintering is 400-600 DEG C；The temperature of three-stage sintering is 700-1200 DEG C.
The present invention originally uses bituminous coal as raw material；The raw material and source metal are cooperated, and described distinctive
Under three-stage sintering mechanism, the cell negative electrode material with excellent electric property can be made.
Preferably, the bituminous coal is coking coal and/or rich coal.
The bituminous coal is preferably the coking coal and/or rich coal pressed in Chinese Coal Classification (GB/T5751-2009).Study table
Face, using the preferred bituminous coal, the electric property of negative electrode material obtained is more excellent.
Preferably, the ash free basis volatile matter content of the coking coal is 10%-28%, caking index 50-65%, glue
Matter layer maximum gauge is≤25%.Preferred difficult to understand Ah's dilation≤150%.
Further preferably, the ash free basis volatile matter content of the coking coal is 15-25%, caking index 55%-60%, glue
Matter layer maximum gauge is 15-20%.
Preferably, the group of the rich coal be divided into ash free basis volatile matter content be 10-37%, caking index be >=
85%, maximum thick ness of plastic layer is > 25%.
Further preferably, the ash free basis volatile matter content of the rich coal is 20-30%, caking index 90%-95%, glue
Matter layer maximum gauge is 30-40%.
Preferably, the miscellaneous element containing at least one of nitrogen, sulphur, P elements in the bituminous coal.Using comprising institute
Stating heteroatomic bituminous coal helps that the superior negative electrode material of performance is made.
Preferably, total content of the miscellaneous element in bituminous coal is no less than 2wt% in the bituminous coal；Further preferably 4
~10wt%.
Preferably, bituminous coal first carries out purification processes before sintering.By purification process, can further be promoted obtained negative
The electric property of pole material.
Preferably, the cigarette pit ash after control purification processes is less than or equal to 0.5%.By the bituminous coal after purification processes
It is sintered with the three-level is carried out again after the source metal mixing, facilitates the property for further promoting negative electrode material obtained
Energy.
In the present invention, to bituminous coal carry out purification process method existing method can be used, present invention preferably employs purification
Processing method is acid system or alkaline process.
Preferably, acid system step are as follows: hydrofluoric acid and sulfuric acid quality will be added to through drying, broken, after screening bituminous coal
It than in the mixed acid solution for 10: 1-1: 10, it is 3-4 that total acid concentration, which is adjusted to pH value, is stirred to react 2-5 hours, passes through at room temperature
Filter is washed to neutrality, and the bituminous coal of acid system after purification is obtained.
Preferably, alkaline process step are as follows: by through drying, broken, after screening bituminous coal is added to mass concentration is 7.5-
In the aqueous solution of 17.5% alkali metal hydroxide and be uniformly mixed, liquid-solid ratio control in 4-8, after standing 2-5 hours
Drying, then under an inert atmosphere, roasts 1-3 hours under conditions of 450-550 DEG C in 105-120 DEG C of drying box, and roasting produces
Object is filtered, washed to neutrality, the bituminous coal after obtaining alkali purification.
In alkaline process purification process, the aqueous solution of the alkali metal hydroxide is preferably sodium hydrate aqueous solution.
Preferably, the source metal is at least one of oxide, salt, hydroxide of transition metal.
Further preferably, the transition metal is at least one of tin, antimony, cobalt, manganese, iron, titanium, chromium, nickel, copper.
Preferably, the source metal is the water soluble salt of the metal, chlorate, the nitric acid of preferably respective metal
Salt, acetate, sulfate etc..
Preferably, the source metal be stannous chloride, antimony chloride, antimony sulfate, antimony hydroxide, cobalt acetate, manganese nitrate,
Manganese acetate, iron chloride, ferric sulfate, ferric nitrate, iron hydroxide, titanium chloride, chromium chloride, nickel chloride, nickel nitrate, nickel sulfate, chlorination
At least one of copper, copper sulphate, copper nitrate.
By after bituminous coal or purification bituminous coal and source metal mix, existing conventional method can be used in hybrid mode, such as stirs
Mix mixing, ball milling mixing, ultrasonic disperse etc.；The ball milling mixing is preferably wet ball grinding mixing.
Preferably, the mass ratio of source metal and bituminous coal is 1: 20~20: 1；It further preferably, is 1: 10~10: 10.
In the present invention, preferably, can be sufficiently mixed in a solvent the source metal of bituminous coal and oxidation processes, it will mix molten
Liquid is dried, and the mixture is obtained.
Solvent is at least one of water, methanol, ethyl alcohol, propyl alcohol, toluene, ether.
In the present invention, existing method is can be used into the dry means of mixed solution.In the present invention, preferably by the mixing
Solution evaporation, dry the mixture.
Preferably, the mixed solution is stirred continuously 2-12 hours at a temperature of 60-85 DEG C, make moisture slow evaporation
Gluing body is formed, drying 6-12 hours in 105-120 DEG C of drying box is then placed into, obtains metal oxide precursor and bituminous coal
Uniform mixture.
In the present invention, sintering process carries out under protective atmosphere；Preferably, the protective atmosphere is, for example, nitrogen
Gas and/or inert gas；The inert gas is at least one of helium, argon gas, neon.
Preferably, the temperature of one-stage sintering is 200-300 DEG C.
Preferably, the heat preservation sintering 1-5h at a temperature of one-stage sintering.
The heating rate of one-stage sintering is 1-10 DEG C/min.
Preferably, the temperature of bis sintering is 500-600 DEG C.
Preferably, the heat preservation sintering 1-5h at a temperature of bis sintering.
Preferably, the temperature of three-stage sintering is 800-1000 DEG C.
Preferably, the heat preservation sintering 1-5h at a temperature of three-stage sintering.
Bis sintering, three-stage sintering heating rate be 1-5 DEG C/min.
Preferably, being crushed to the material of sintering, sieving processing, the cell negative electrode material is obtained.
Using bituminous coal as raw material by broken, screening, purification, oxide precursor is added in preparation method provided by the invention
And three-stage pyrolysis step and obtain.It is preferably based on the preparation method of the cell negative electrode material of bituminous coal, comprising the following steps:
Step 1: the bituminous coal as raw material is dried, broken and screening, partial size is obtained in 20 microns of coal dusts below
Particle；
Step 2: the bituminous coal particle obtained in step 1 is carried out purification processes by acid system or alkali process, cigarette is removed
Metal impurities in coal obtain purifying bituminous coal of the ash content less than 0.5%；
Step 3: being added to the bituminous coal in step 2 after purification according to 1: 20-20: 1 ratio containing the molten of source metal
It in liquid, is stirred continuously at a temperature of 60-85 DEG C 2-12 hours, so that moisture slow evaporation is formed gluing body, be then placed into 105-
Drying 6-12 hours, obtain mixture in 120 DEG C of drying boxes；
Step 4: the mixture obtained in step 3 is put into the sintering furnace for be connected with inert atmosphere successively through 200-300
DEG C one-stage sintering, the bis sintering at 400-600 DEG C and the three-stage sintering at 700-1200 DEG C；Room is cooled to after the completion of sintering
Wen Hou, takes out sintering feed, and sintering feed obtains the composite negative pole material through broken and classification.
Preferably, drying temperature is 105 DEG C -120 DEG C in the first step, drying time is 10-12 hours, is crushed
Mode is preferably after swing crushing crusher machine 30s-5min again through planetary ball mill ball milling 6-10 hours.
Preferably, in three-stage pyrolytic process, inert atmosphere is selected from helium, argon gas, neon, nitrogen in the 4th step
At least one of gas, the temperature increasing schedule of the heat treatment of three-stage pyrolysis are to rise to 200- with the heating rate of 1-10 DEG C/min
After 300 DEG C, heat preservation 1-5 hours, then 400-600 DEG C of sintering 1-5 hours risen to the heating rate of 1-5 DEG C/min, finally with 1-5
DEG C/heating rate of min rises to 700-1200 DEG C of sintering 1-5 hours.
The present invention also provides a kind of using composite negative pole material made from the preparation method.
Composite negative pole material of the present invention, including bituminous coal pyrolytic carbon；Nano metal particles are distributed in bituminous coal pyrolytic carbon
Son and/or metal oxide nano particles.
The composite negative pole material, the nano-metal-oxide be tin oxide, antimony oxide, cobalt oxide, manganese oxide,
At least one of iron oxide, titanium oxide, chromium oxide, nickel oxide, copper oxide, zinc oxide.The nano metal ion is gold
Belong to the corresponding simple substance that oxide in-situ restores.
Product of the bituminous coal pyrolytic carbon by bituminous coal through described one section, two sections and three-stage sintering.
Preferably, the partial size of the composite negative pole material is 5-25 microns.
Preferably, the composite negative pole material, including bituminous coal pyrolytic carbon；Nano metal is distributed in bituminous coal pyrolytic carbon
Particle and metal oxide nano particles.
Preferred composite negative pole material by bituminous coal pyrolytic carbon and provides the nano metal particles and nano metal oxygen of high capacity
Compound particle composition, nano metal particles and the metal oxide nano particles in-situ preparation in bituminous coal pyrolytic carbon, and uniformly divide
It is dispersed in bituminous coal pyrolytic carbon, there are a large amount of ducts and gaps in bituminous coal pyrolytic carbon.
Preferably, the composite negative pole material, bituminous coal pyrolytic carbon and nano metal particles and nano-metal-oxide
Mass ratio be 1: 1: 1~20:1: 20.
The present invention also provides the applications of the composite negative pole material described in one kind, are used to prepare the cathode of lithium ion battery.
Composite negative pole material of the present invention is preferably lithium ion battery negative material.
In the present invention, existing method can be used, using cell negative electrode material of the present invention as negative electrode active ingredient,
It is assembled into the cathode of lithium ion battery.
The principle of the invention and feature:
Carbon content is 74-92%, volatile matter content 18-26% in bituminous coal, and contains organic members such as a certain amount of N, P, S
Element.In pyrolytic process, it is capable of forming the three-phase object composition gel that gas-liquid-solid interpenetrates, to utilize bituminous coal pyrolytic process
The mechanism of middle bonding coking prepares the compound lithium ion battery negative material of carbon-metal oxide.In three-stage pyrolytic process, the
One section occurs at a lower temperature (- 300 DEG C of room temperature), at this point, limited heat effect occurs for the initial molecule structure of bituminous coal, mainly
For the removing of moisture, in the process, oxide precursor in liquid phase from crystallizing and be stably dispersed between bituminous coal particle；Second
Duan Fasheng at moderate temperatures (about 500 DEG C), at this point, forming thick gas, liquid, solid three-phase containing the bituminous coal of appropriate gel
Coexisting mixture, the oxide precursor being added are easy to be dispersed in the gel liquid phase, and melting then occurs, glues
Knot forms the semicoke containing oxide precursor；(700 DEG C or more) are pyrolyzed by the third section under higher temperature, bituminous coal can be made
Further polycondensation reaction occurs, generates the very high coal tar of carbon content, simultaneous oxidation object presoma thermally decomposes, and forms nanometer
Oxide.At a higher temperature, coal tar is chemically reacted with oxide, by its partial reduction at metal, ultimately form by
Bituminous coal pyrolytic carbon and the high-capacity cathode material for dispersing nano metal particles and nano-oxide particles composition inside it.Mesh
Before until, the article (or patent) for preparing lithium ion cell high-capacity metal oxide-type negative electrode material based on bituminous coal rarely has report
Road.
The beneficial effects of the present invention are as follows:
(1) pyrolysis of the bituminous coal and pyrolysis of oxide precursor is synchronous occurs, and bituminous coal thermal decomposition product and oxide precursor
Mutual redox reaction can occur to a certain extent for body thermal decomposition product, so that oxide and its reducing metal product can
It is evenly dispersed in bituminous coal pyrolytic carbon, and keep combining closely between carbon shell.
(2) bituminous coal pyrolytic carbon plays the role of separation oxide granular precursor as carbon skeleton, and generates in presoma
It during oxide and metallic particles, limits its forming core and grows up, be easy to get the nano-oxide and nano metal that do not reunite
Particle largely alleviates the bulking effect in charge and discharge process.
(3) protective layer that bituminous coal pyrolytic carbon is formed can effectively improve the electric conductivity of material and avoid internal nano metal particles
And nano-oxide particles directly contact a large amount of generations for causing SEI film with electrolyte；In addition, containing a certain amount of in bituminous coal
Nitrogen, sulphur, P elements realize doping in situ in pyrolytic process, further increase electric conductivity.
(4) in bituminous coal pyrolytic process, contained volatile matter (macromolecule organic) is acutely decomposed at high temperature, is generated and is discharged
A large amount of gaseous volatiles can form the porous structure with a large amount of apertures and gap, these apertures and sky in bituminous coal pyrolytic carbon
Gap provides the memory space of electrolyte, shortens ion transmission path, improves high rate performance.
(5) obtain lithium ion battery negative material capacity height, good rate capability, have extended cycle life；Bituminous coal feedstock source
Extensively, low in cost；Preparation process is simple, is easy to control, and yield is high.
Detailed description of the invention
Fig. 1 is 1 cathode material for high capacity lithium ion battery SEM of embodiment of the present invention figure
Fig. 2 is 1 cathode material for high capacity lithium ion battery XRD diagram of the embodiment of the present invention
From in attached drawing 1 it can be seen that metal oxide is dispersed in bituminous coal pyrolytic carbon, and it is close between carbon shell
In conjunction with, meanwhile, there are a large amount of gaps in bituminous coal pyrolytic carbon lamellar structure.
From in attached drawing 2 it can be seen that mainly containing in the composite negative pole material that is formed after three-stage is pyrolyzed of oxide and carbon
There are two kinds of object phases of manganese oxide and agraphitic carbon.
Specific embodiment
Embodiment 1
(1) it is 52% that selection ash free basis volatile matter content 15%, which is caking index, maximum thick ness of plastic layer 25%, institute
The coking coal of hetero atom N, S, P and content of heteroatoms 4% for containing are former by coking coal of the 100g after 120 DEG C of dry 10h as raw material
Material is put into vibrating pulverizer and is crushed after 1min again through planetary ball mill ball milling 6 hours, is sieved, is taken under sieve with 500 meshes
Object.
(2) 50g is added to the nitration mixture that hydrofluoric acid and sulfuric acid mass ratio are 10: 1 through drying, broken, after screening coking coal
In solution, liquid-solid ratio 4, it is 3 that total acid concentration, which is adjusted to pH value, is stirred to react 2 hours, is filtered, washed to neutrality at room temperature,
The coking coal of acid system after purification is obtained, coking coal ash content is 0.37% after purification.
(3) 10g manganese acetate is dissolved in 100ml aqueous solution, the coking coal ultrasonic disperse 3h of 20g after purification is added, after mixing
Material be stirred continuously 2 hours at a temperature of at 60 DEG C, so that moisture slow evaporation is formed gluing body, be then placed into 120 DEG C it is dry
Drying 6 hours, obtain the homogeneous mixture of metal oxide precursor and coking coal in dry case.
(4) mixture after taking 10g dry is placed in graphite Noah's ark, in the Muffle furnace of nitrogen atmosphere protection with 1 DEG C/
After the heating rate of min rises to 200 DEG C of heat preservations 1 hour, 500 DEG C then are risen to the heating rate of 1 DEG C/min and is sintered 1 hour,
800 DEG C finally are risen to the heating rate of 1 DEG C/min to be sintered 1 hour, are taken out after being cooled to room temperature.Sintered sample is passed through
Swing crushing crusher machine 1min carries out second-time breakage, and then the sample after second-time breakage is averaged through multi-stage oscillating screen point
The cell negative electrode material based on coking coal that partial size is 18 microns.
Embodiment 2
(1) it is 62% that selection ash free basis volatile matter content 25%, which is caking index, maximum thick ness of plastic layer 25%, institute
The coking coal of hetero atom N, S, P and content of heteroatoms 10% for containing are as raw material, by coking coal of the 100g after 120 DEG C of dry 12h
Raw material is put into vibrating pulverizer and is crushed after 10min again through planetary ball mill ball milling 10 hours, is sieved, is taken with 500 meshes
Screenings.
(2) by 50g through drying, that broken, after screening coking coal is added to the nitration mixture that hydrofluoric acid and sulfuric acid mass ratio are 2: 1 is molten
In liquid, liquid-solid ratio 6, it is 4 that total acid concentration, which is adjusted to pH value, is stirred to react 5 hours at room temperature, is filtered, washed to neutrality, is obtained
To the coking coal of acid system after purification, coking coal ash content is 0.42% after purification.
(3) 20g manganese acetate is dissolved in 100ml aqueous solution, and the coking coal ultrasonic disperse 3h of 1g after purification is added, mixed
Material is stirred continuously 12 hours at a temperature of at 85 DEG C, so that moisture slow evaporation is formed gluing body, is then placed into 120 DEG C of dryings
Drying 12 hours, obtain the homogeneous mixture of metal oxide precursor and coking coal in case.
(4) mixture after taking 10g dry is placed in graphite Noah's ark, in the Muffle furnace of nitrogen atmosphere protection with 5 DEG C/
After the heating rate of min rises to 300 DEG C of heat preservations 5 hours, 600 DEG C then are risen to the heating rate of 5 DEG C/min and is sintered 5 hours,
1000 DEG C finally are risen to the heating rate of 5 DEG C/min to be sintered 5 hours, are taken out after being cooled to room temperature.By sintered sample
Second-time breakage is carried out through swing crushing crusher machine 5min, is then put down the sample after second-time breakage through multi-stage oscillating screen point
The cell negative electrode material based on coking coal that equal partial size is 18 microns.
Embodiment 3
(1) it is 58% that selection ash free basis volatile matter content 20%, which is caking index, maximum thick ness of plastic layer 18%, institute
The coking coal of hetero atom N, S, P and content of heteroatoms 8% for containing are former by bituminous coal of the 100g after 105 DEG C of dry 10h as raw material
Material is put into vibrating pulverizer and is crushed after 5min again through planetary ball mill ball milling 8 hours, is sieved, is taken under sieve with 500 meshes
Object.
(2) 50g is added to the nitration mixture that hydrofluoric acid and sulfuric acid mass ratio are 10: 1 through drying, broken, after screening coking coal
In solution, liquid-solid ratio 5, it is 3 that total acid concentration, which is adjusted to pH value, is stirred to react 5 hours, is filtered, washed to neutrality at room temperature,
The coking coal of acid system after purification is obtained, coking coal ash content is 0.23% after purification.
(3) 10g manganese acetate is dissolved in 100ml aqueous solution, the coking coal ultrasonic disperse 3h of 50g after purification is added, after mixing
Material be stirred continuously 6 hours at a temperature of at 70 DEG C, so that moisture slow evaporation is formed gluing body, be then placed into 105 DEG C it is dry
Drying 10 hours, obtain the homogeneous mixture of metal oxide precursor and coking coal in dry case.
(4) mixture after taking 10g dry is placed in graphite Noah's ark, in the Muffle furnace of nitrogen atmosphere protection with 3 DEG C/
After the heating rate of min rises to 250 DEG C of heat preservations 3 hours, 550 DEG C then are risen to the heating rate of 3 DEG C/min and is sintered 3 hours,
900 DEG C finally are risen to the heating rate of 3 DEG C/min to be sintered 3 hours, are taken out after being cooled to room temperature.Sintered sample is passed through
Swing crushing crusher machine 3min carries out second-time breakage, and then the sample after second-time breakage is averaged through multi-stage oscillating screen point
The cell negative electrode material based on coking coal that partial size is 18 microns.
Embodiment 4
(1) it is 95% that selection ash free basis volatile matter content 25%, which is caking index, maximum thick ness of plastic layer 35%, institute
The rich coal of hetero atom N, S, P and content of heteroatoms 8% for containing are former by rich coal of the 100g after 105 DEG C of dry 10h as raw material
Material is put into vibrating pulverizer and is crushed after 4min again through planetary ball mill ball milling 8 hours, is sieved, is taken under sieve with 500 meshes
Object.
(2) 50g is added to the nitration mixture that hydrofluoric acid and sulfuric acid mass ratio are 10: 1 through drying, broken, after screening rich coal
In solution, liquid-solid ratio 6, it is 3 that total acid concentration, which is adjusted to pH value, is stirred to react 4 hours, is filtered, washed to neutrality at room temperature,
The rich coal of acid system after purification is obtained, rich coal ash content is 0.33% after purification.
(3) 10g stannous chloride is dissolved in 100ml aqueous solution, and the rich coal ultrasonic disperse 3h of 50g after purification, mixing is added
Material afterwards is stirred continuously 8 hours at a temperature of at 70 DEG C, so that moisture slow evaporation is formed gluing body, is then placed into 120 DEG C
Drying 10 hours, obtain the homogeneous mixture of metal oxide precursor and rich coal in drying box.
(4) mixture after taking 10g dry is placed in graphite Noah's ark, in the Muffle furnace of nitrogen atmosphere protection with 3 DEG C/
After the heating rate of min rises to 250 DEG C of heat preservations 3 hours, 550 DEG C then are risen to the heating rate of 3 DEG C/min and is sintered 3 hours,
900 DEG C finally are risen to the heating rate of 3 DEG C/min to be sintered 3 hours, are taken out after being cooled to room temperature.Sintered sample is passed through
Swing crushing crusher machine 3min carries out second-time breakage, and then the sample after second-time breakage is averaged through multi-stage oscillating screen point
The cell negative electrode material based on rich coal that partial size is 18 microns.
Embodiment 5
(1) it is 58% that selection ash free basis volatile matter content 20%, which is caking index, maximum thick ness of plastic layer 18%, institute
The coking coal of hetero atom N, S, P and content of heteroatoms 8% for containing are former by coking coal of the 100g after 120 DEG C of dry 12h as raw material
Material is put into vibrating pulverizer and is crushed after 5min again through planetary ball mill ball milling 8 hours, is sieved, is taken under sieve with 500 meshes
Object.
(2) sodium hydrate aqueous solution for being 10% to mass concentration is added through drying, broken, after screening coking coal in 50g
In and be uniformly mixed, liquid-solid ratio control is dried after standing 4 hours in 120 DEG C of drying boxes 6, then under an inert atmosphere,
It is roasted 3 hours under conditions of 500 DEG C, product of roasting is filtered, washed to neutrality, the bituminous coal after obtaining alkali purification, after purification
Bituminous coal ash content is 0.47%.
(3) 10g stannous chloride is dissolved in 100ml aqueous solution, and the coking coal ultrasonic disperse 3h of 50g after purification, mixing is added
Material afterwards is stirred continuously 8 hours at a temperature of at 70 DEG C, so that moisture slow evaporation is formed gluing body, is then placed into 120 DEG C
Drying 10 hours, obtain the homogeneous mixture of metal oxide precursor and bituminous coal in drying box.
(4) mixture after taking 10g dry is placed in graphite Noah's ark, in the Muffle furnace of nitrogen atmosphere protection with 3 DEG C/
After the heating rate of min rises to 300 DEG C of heat preservations 3 hours, 600 DEG C then are risen to the heating rate of 3 DEG C/min and is sintered 3 hours,
900 DEG C finally are risen to the heating rate of 5 DEG C/min to be sintered 3 hours, are taken out after being cooled to room temperature.Sintered sample is passed through
Swing crushing crusher machine 5min carries out second-time breakage, and then the sample after second-time breakage is averaged through multi-stage oscillating screen point
The cell negative electrode material based on coking coal that partial size is 18 microns.
Embodiment 6:
1) choosing ash free basis volatile matter content is 15%, caking index 58%, and maximum thick ness of plastic layer 25% is contained
Hetero atom N, S, P and content of heteroatoms 8% coking coal as raw material, by coking coal raw material of the 100g after 120 DEG C of dry 10h
It is put into vibrating pulverizer to be crushed after 5min again through planetary ball mill ball milling 8 hours, be sieved with 500 meshes, extracting screen underflow.
(2) 50g is added to the nitration mixture that hydrofluoric acid and sulfuric acid mass ratio are 10: 1 through drying, broken, after screening coking coal
In solution, liquid-solid ratio 6, it is 3 that total acid concentration, which is adjusted to pH value, is stirred to react 4 hours, is filtered, washed to neutrality at room temperature,
The coking coal of acid system after purification is obtained, coking coal ash content is 0.22% after purification.
(3) 10g stannous chloride is dissolved in 100ml aqueous solution, and the coking coal ultrasonic disperse 3h of 50g after purification, mixing is added
Material afterwards is stirred continuously 8 hours at a temperature of at 70 DEG C, so that moisture slow evaporation is formed gluing body, is then placed into 120 DEG C
Drying 10 hours, obtain the homogeneous mixture of metal oxide precursor and coking coal in drying box.
(4) mixture after taking 10g dry is placed in graphite Noah's ark, in the Muffle furnace of nitrogen atmosphere protection with 3 DEG C/
After the heating rate of min rises to 250 DEG C of heat preservations 3 hours, 550 DEG C then are risen to the heating rate of 3 DEG C/min and is sintered 3 hours,
900 DEG C finally are risen to the heating rate of 3 DEG C/min to be sintered 3 hours, are taken out after being cooled to room temperature.Sintered sample is passed through
Swing crushing crusher machine 3min carries out second-time breakage, and then the sample after second-time breakage is averaged through multi-stage oscillating screen point
The cell negative electrode material based on coking coal that partial size is 18 microns.
Comparative example 1
This comparative example, which is inquired into, uses anthracite, and concrete operations are as follows:
(1) with dry ash free basis volatile matter content for 6.9%, the anthracite that dry ash free basis hydrogen content is 4% is as former
Anthracite raw material of the 100g after 120 DEG C of dry 12h is put into vibrating pulverizer and is crushed after 5min again through planetary ball mill by material
It ball milling 8 hours, is sieved with 500 meshes, extracting screen underflow.
(2) by 50g through drying, broken, after screening anthracite be added to hydrofluoric acid and sulfuric acid mass ratio be 10: 1 it is mixed
In acid solution, liquid-solid ratio 6, it is 3 that total acid concentration, which is adjusted to pH value, is stirred to react at room temperature 4 hours, through being filtered, washed into
Property, the anthracite of acid system after purification is obtained, smokeless ash content of coal is 0.24% after purification.
(3) 10g manganese acetate is dissolved in 100ml aqueous solution, and the anthracite ultrasonic disperse 3h of 50g after purification, mixing is added
Material afterwards is stirred continuously 8 hours at a temperature of at 70 DEG C, so that moisture slow evaporation is formed gluing body, is then placed into 120 DEG C
Drying 6 hours, obtain metal oxide precursor and anthracitic homogeneous mixture in drying box.
(4) mixture after taking 10g dry is placed in graphite Noah's ark, in the Muffle furnace of nitrogen atmosphere protection with 5 DEG C/
After the heating rate of min rises to 200 DEG C of heat preservations 3 hours, 500 DEG C then are risen to the heating rate of 5 DEG C/min and is sintered 3 hours,
900 DEG C finally are risen to the heating rate of 5 DEG C/min to be sintered 3 hours, are taken out after being cooled to room temperature.Sintered sample is passed through
Swing crushing crusher machine 3min carries out second-time breakage, and then the sample after second-time breakage is averaged through multi-stage oscillating screen point
Partial size is 18 microns based on anthracitic cell negative electrode material.
Comparative example 2:
This comparative example, which is inquired into, uses lignite, and concrete operations are as follows:
1) choosing ash free basis volatile matter content is 40%, the lignite of contained hetero atom N, S, P and content of heteroatoms 6%
As raw material, lignite raw material of the 100g after 120 DEG C of dry 10h is put into vibrating pulverizer and is crushed after 5min again through planetary ball
It grinding machine ball milling 8 hours, is sieved with 500 meshes, extracting screen underflow.
(2) 50g is added to the nitration mixture that hydrofluoric acid and sulfuric acid mass ratio are 10: 1 through drying, broken, after screening lignite
In solution, liquid-solid ratio 6, it is 3 that total acid concentration, which is adjusted to pH value, is stirred to react 4 hours, is filtered, washed to neutrality at room temperature,
The lignite of acid system after purification is obtained, lignite ash is divided into 0.22% after purification.
(3) 10g manganese acetate is dissolved in 100ml aqueous solution, the lignite ultrasonic disperse 3h of 50g after purification is added, after mixing
Material be stirred continuously 8 hours at a temperature of at 70 DEG C, so that moisture slow evaporation is formed gluing body, be then placed into 120 DEG C it is dry
Drying 10 hours, obtain the homogeneous mixture of metal oxide precursor and lignite in dry case.
(4) mixture after taking 10g dry is placed in graphite Noah's ark, in the Muffle furnace of nitrogen atmosphere protection with 3 DEG C/
After the heating rate of min rises to 250 DEG C of heat preservations 3 hours, 550 DEG C then are risen to the heating rate of 3 DEG C/min and is sintered 3 hours,
900 DEG C finally are risen to the heating rate of 3 DEG C/min to be sintered 3 hours, are taken out after being cooled to room temperature.Sintered sample is passed through
Swing crushing crusher machine 3min carries out second-time breakage, and then the sample after second-time breakage is averaged through multi-stage oscillating screen point
The cell negative electrode material based on lignite that partial size is 18 microns.
Comparative example 3
This comparative example is inquired into, and does not calcine mechanism using three-stage of the presently claimed invention, and concrete operations are as follows:
(1) it is 58% that selection ash free basis volatile matter content 20%, which is caking index, maximum thick ness of plastic layer 18%, institute
The coking coal of hetero atom N, S, P and content of heteroatoms 8% for containing as raw material, by coking coal of the 100g after 120 DEG C of dry 12h
Raw material is put into vibrating pulverizer and is crushed after 5min again through planetary ball mill ball milling 8 hours, is sieved with 500 meshes, takes sieve
Lower object.
(2) 50g is added to the nitration mixture that hydrofluoric acid and sulfuric acid mass ratio are 10: 1 through drying, broken, after screening coking coal
In solution, liquid-solid ratio 5, it is 3 that total acid concentration, which is adjusted to pH value, is stirred to react 4 hours, is filtered, washed to neutrality at room temperature,
The coking coal of acid system after purification is obtained, coking coal ash content is 0.23% after purification.
(3) 10g manganese acetate is dissolved in 100m1 aqueous solution, the coking coal ultrasonic disperse 3h of 50g after purification is added, after mixing
Material be stirred continuously 8 hours at a temperature of at 70 DEG C, so that moisture slow evaporation is formed gluing body, be then placed into 120 DEG C it is dry
Drying 6 hours, obtain the homogeneous mixture of metal oxide precursor and coking coal in dry case.
(4) mixture after taking 10g dry is placed in graphite Noah's ark, in the Muffle furnace of nitrogen atmosphere protection with 5 DEG C/
The heating rate of min rises to 1000 DEG C and keeps the temperature 3 hours, takes out after being cooled to room temperature.By sintered sample through swing crushing
Crusher machine 5min carries out second-time breakage, and then by the sample after second-time breakage through multi-stage oscillating screen point, obtaining average grain diameter is 18
The cell negative electrode material based on coking coal of micron.
Comparative example 4
This comparative example is inquired into, and is added without oxide precursor, concrete operations are as follows:
(1) it is 58% that selection ash free basis volatile matter content 20%, which is caking index, maximum thick ness of plastic layer 18%, institute
The coking coal of hetero atom N, S, P and content of heteroatoms 8% for containing as raw material, by coking coal of the 100g after 120 DEG C of dry 12h
Raw material is put into vibrating pulverizer and is crushed after 5min again through planetary ball mill ball milling 8 hours, is sieved with 500 meshes, takes sieve
Lower object.
(2) 50g is added to the nitration mixture that hydrofluoric acid and sulfuric acid mass ratio are 10: 1 through drying, broken, after screening coking coal
In solution, liquid-solid ratio 5, it is 3 that total acid concentration, which is adjusted to pH value, is stirred to react 4 hours, is filtered, washed to neutrality at room temperature,
The coking coal of acid system after purification is obtained, coking coal ash content is 0.22% after purification.
(3) coking coal of 10g after purification is dissolved in ultrasonic disperse 3h in 100ml aqueous solution, it is evenly dispersed after in 70 DEG C of temperature
It is stirred continuously under degree 4 hours, moisture slow evaporation is made to form gluing body, be then placed into drying 6 hours in 120 DEG C of drying boxes,
Obtain uniformly mixed solid coking coal material.
(4) mixture after taking 10g dry is placed in graphite Noah's ark, in the Muffle furnace of nitrogen atmosphere protection with 5 DEG C/
After the heating rate of min rises to 200 DEG C of heat preservations 3 hours, 500 DEG C then are risen to the heating rate of 5 DEG C/min and is sintered 3 hours,
900 DEG C finally are risen to the heating rate of 5 DEG C/min to be sintered 3 hours, are taken out after being cooled to room temperature.Sintered sample is passed through
Swing crushing crusher machine 5min carries out second-time breakage, and then the sample after second-time breakage is averaged through multi-stage oscillating screen point
The cell negative electrode material based on coking coal that partial size is 18 microns.
Comparative example 5
This comparative example is inquired into, and content of heteroatoms is less in raw material coking coal, and concrete operations are as follows:
(1) it is 60% that selection ash free basis volatile matter content 22%, which is caking index, maximum thick ness of plastic layer 20%, institute
The coking coal of hetero atom N, S, P and content of heteroatoms 1% for containing as raw material, by coking coal of the 100g after 120 DEG C of dry 12h
Raw material is put into vibrating pulverizer and is crushed after 5min again through planetary ball mill ball milling 8 hours, is sieved with 500 meshes, takes sieve
Lower object.
(2) by 50g through drying, the nitration mixture that broken, after screening coking coal is added to hydrofluoric acid and sulfuric acid mass ratio is 10:1
In solution, liquid-solid ratio 5, it is 3 that total acid concentration, which is adjusted to pH value, is stirred to react 4 hours, is filtered, washed to neutrality at room temperature,
The coking coal of acid system after purification is obtained, coking coal ash content is 0.22% after purification.
(3) 10g manganese acetate is dissolved in 100ml aqueous solution, the coking coal ultrasonic disperse 3h of 50g after purification is added, after mixing
Material be stirred continuously 8 hours at a temperature of at 70 DEG C, so that moisture slow evaporation is formed gluing body, be then placed into 120 DEG C it is dry
Drying 6 hours, obtain the homogeneous mixture of metal oxide precursor and coking coal in dry case.
(4) mixture after taking 10g dry is placed in graphite Noah's ark, in the Muffle furnace of nitrogen atmosphere protection with 5 DEG C/
After the heating rate of min rises to 200 DEG C of heat preservations 3 hours, 500 DEG C then are risen to the heating rate of 5 DEG C/min and is sintered 3 hours,
900 DEG C finally are risen to the heating rate of 5 DEG C/min to be sintered 3 hours, are taken out after being cooled to room temperature.Sintered sample is passed through
Swing crushing crusher machine 5min carries out second-time breakage, and then the sample after second-time breakage is averaged through multi-stage oscillating screen point
The cell negative electrode material based on coking coal that partial size is 18 microns.
The electric property of each embodiment and comparative example is measured, test method is as follows:
(1) preparation process of electrode: by the active material prepared, PVDF, conductive black (acetylene black) with 8: 1: 1 matter
Amount adds a certain amount of N-Methyl pyrrolidone (NMP) than mixing, is sufficiently mixed in the agate mortar uniformly.It will mix equal
Even slurry is uniformly coated on copper foil, after the completion of coating, the copper foil for being coated with slurry is dry in 120 DEG C of vacuum ovens
12 hours.After the completion of drying, electrode slice is cut out into the disk for 12mm, electrode slice is weighed mark later, drying is placed on gloves
It is spare in case.
(2) test of chemical property, institute the assembling process of battery: are carried out in experiment to material using button-shaped half-cell
Battery assembly be all to be carried out in glove box under an argon atmosphere, require the detection of water oxygen value to be consistently less than in assembling process
0.1ppm, in assembling process, electrolyte uses commercialization 1mol L-1Lithium hexafluorophosphate electrolyte solution as lithium ion battery be electrolysed
Liquid, polypropylene (PP) diaphragm is as the diaphragm of lithium ion battery, and lithium ion battery is using lithium piece as to electrode；All batteries all groups
2025 type button cells are dressed up, and are sealed in glove box with battery sealing machine.Battery assembly is according to negative electrode casing-pole piece electricity
Solve liquid-diaphragm-electrolyte-lithium piece-nickel sheet-anode cover assembled in sequence.
Test result is shown in Table 1:
1 Examples 1 to 5 of table and comparative example 1~5 are to the electrochemical property test result in lithium half-cell
By electrochemical property test result it is found that Examples 1 to 6 has good comprehensive electrochemical.
Due to using anthracite for raw material in comparative example 1, volatile matter is too low and gel quantity is few, in high-temperature heat treatment mistake
Mobility is poor in journey, does not bond, so that the nano-oxide being added can not disperse wherein, cannot be formed and effectively be led
Electric skeleton, and then chemical property is poor.
Due to using lignite for raw material in comparative example 2, volatile matter is excessively high, can expand in high-temperature heat treatment process,
Equally make material coking behavior bad, the nano-metal-oxide/carbon compound cathode materials uniformly coated can not be formed, influence electricity
Chemical property plays.
Due to not using three-stage to be pyrolyzed in comparative example 3, so that coking coal, in pyrolytic process, coking speed is difficult to control,
Obtained pyrolytic carbon is difficult to equably coat nano-metal-oxide, therefore chemical property is poor.
Due to being added without oxide precursor in comparative example 4, high capacity oxide cannot be formed in negative electrode material and is gone back
Virgin metal particle, therefore capacity is lower.
In comparative example 5 due in coking coal content of heteroatoms it is lower, and coking coal ash free basis volatile matter content, caking index, matter
Layer maximum gauge cannot generate the nano-metal-oxide uniformly coated and offer except preferred scope in negative electrode material
Good electric conductivity, therefore chemical property is poor.
Claims (10)
1. a kind of preparation method of the composite negative pole material of metal-carbon, which is characterized in that bituminous coal is mixed to obtain to mixing with source metal
Material；Mixture is successively through one-stage sintering, bis sintering and three-stage sintering；Obtain the composite negative pole material；Wherein, one section of burning
The temperature of knot is for 300 DEG C and following；The temperature of bis sintering is 400~600 DEG C；The temperature of three-stage sintering is 700~1200 DEG C.
2. the preparation method of the composite negative pole material of metal-carbon as described in claim 1, which is characterized in that the bituminous coal
For coking coal and/or rich coal；
The ash free basis volatile matter content of preferred coking coal is 10-28%, caking index 50-65%, and maximum thick ness of plastic layer is
≤ 25%；
It is 10-37% that the group of preferred rich coal, which is divided into ash free basis volatile matter content, and caking index is >=85%, and gelatinous layer is maximum thick
Degree is > 25%.
3. the preparation method of the composite negative pole material of metal-carbon as claimed in claim 1 or 2, which is characterized in that the cigarette
Miscellaneous element containing at least one of nitrogen, sulphur, P elements in coal；Total content of the miscellaneous element in bituminous coal is no less than 2wt%.
4. the preparation method of the composite negative pole material of metal-carbon as claimed in any one of claims 1 to 3, which is characterized in that cigarette
Coal first carries out purification processes before sintering, and the cigarette pit ash after controlling purification processes is less than or equal to 0.5%；
The purification processing method is preferably acid system or alkaline process；Wherein,
Acid system step are as follows: by through drying, broken, after screening bituminous coal is added to hydrofluoric acid and sulfuric acid mass ratio is 10: 1-1: 10
Mixed acid solution in, total acid concentration be adjusted to pH value be 3-4, be stirred to react 2-5 hours, be filtered, washed to neutrality at room temperature,
Obtain the bituminous coal of acid system after purification；
Alkaline process step are as follows: the alkali metal hydrogen for being 7.5-17.5% to mass concentration will be added through drying, broken, after screening bituminous coal
It in oxide water solution and is uniformly mixed, liquid-solid ratio control is dried in 105-120 DEG C of drying box after standing 2-5 hours in 4-8
It is dry, then under an inert atmosphere, roasted 1-3 hours under conditions of 450-550 DEG C, product of roasting is filtered, washed to neutrality,
Bituminous coal after obtaining alkali purification.
5. the preparation method of the composite negative pole material of metal-carbon as described in claim 1, which is characterized in that the metal
Source is at least one of oxide, salt, hydroxide of transition metal；The transition metal be tin, antimony, cobalt, manganese, iron,
At least one of titanium, chromium, nickel, copper.
6. the preparation method of the composite negative pole material of metal-carbon as claimed in claim 1 or 5, which is characterized in that by bituminous coal with
Source metal mixes in a solvent, obtains mixed solution；By the described mixed solution evaporation, dry the mixture；
Solvent is at least one of water, methanol, ethyl alcohol, propyl alcohol, toluene, ether.
7. the preparation method of the composite negative pole material of metal-carbon as claimed in claim 6, which is characterized in that source metal and cigarette
The mass ratio of coal is 1: 20-20: 1.
8. the preparation method of the composite negative pole material of metal-carbon as described in claim 1, which is characterized in that described one
Heat preservation sintering 1-5h under section sintering temperature；The heat preservation sintering 1-5h at a temperature of bis sintering；In the three-stage sintering
At a temperature of heat preservation sintering 1-5h.
9. composite negative pole material made from a kind of described in any item preparation methods of claim 1-8；It is characterised in that it includes cigarette
Pyrolysis of coal carbon；Nano metal particles and/or metal oxide nano particles are distributed in bituminous coal pyrolytic carbon.
10. a kind of application of composite negative pole material as claimed in claim 9, which is characterized in that be used to prepare lithium ion battery
Cathode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810057247.5A CN110061199B (en) | 2018-01-19 | 2018-01-19 | Metal-carbon composite anode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810057247.5A CN110061199B (en) | 2018-01-19 | 2018-01-19 | Metal-carbon composite anode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110061199A true CN110061199A (en) | 2019-07-26 |
| CN110061199B CN110061199B (en) | 2023-08-01 |
Family
ID=67315271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810057247.5A Active CN110061199B (en) | 2018-01-19 | 2018-01-19 | Metal-carbon composite anode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110061199B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115722224A (en) * | 2022-09-12 | 2023-03-03 | 遂宁碳基环保科技有限公司 | Carbon-supported transition metal catalyst for sewage treatment and preparation method and application thereof |
| CN115744896A (en) * | 2022-11-30 | 2023-03-07 | 湖南宸宇富基新能源科技有限公司 | Artificial graphite @ crystalline flake graphite @ amorphous carbon composite active material and preparation and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59141408A (en) * | 1983-01-28 | 1984-08-14 | Sumitomo Metal Ind Ltd | Production of high-purity carbon material |
| CN101450865A (en) * | 2007-12-07 | 2009-06-10 | 中国科学院金属研究所 | Heat treating method of carbon graphite material |
| CN101997110A (en) * | 2009-08-19 | 2011-03-30 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing stannum-carbon composite cathode material for lithium ion battery by utilizing thermal carbon reduction method |
| CN103066243A (en) * | 2012-12-06 | 2013-04-24 | 中南大学 | Coke powder-based cathode material of lithium ion power battery and preparation method thereof |
| CN105185997A (en) * | 2015-10-27 | 2015-12-23 | 中国科学院物理研究所 | Sodion secondary battery negative electrode material and preparing method and application thereof |
| KR20160068566A (en) * | 2014-12-05 | 2016-06-15 | 주식회사 포스코 | Method and apparatus for producing binder for coke |
| CN106099124A (en) * | 2016-07-19 | 2016-11-09 | 辽宁科技大学 | A kind of preparation method of coal base hydrogen reduction carbon catalysis material |
| CN106229519A (en) * | 2016-07-29 | 2016-12-14 | 辽宁科技大学 | A kind of method utilizing coal to prepare auto-dope difunctional oxygen reaction eelctro-catalyst |
| CN107180958A (en) * | 2017-06-05 | 2017-09-19 | 三峡大学 | A kind of anthracite/silicon monoxide/amorphous carbon negative material and preparation method thereof |
| CN107342409A (en) * | 2017-06-29 | 2017-11-10 | 三峡大学 | A kind of high-performance anthracite/silicon monoxide/phosphorus composite negative pole material and preparation method thereof |
-
2018
- 2018-01-19 CN CN201810057247.5A patent/CN110061199B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59141408A (en) * | 1983-01-28 | 1984-08-14 | Sumitomo Metal Ind Ltd | Production of high-purity carbon material |
| CN101450865A (en) * | 2007-12-07 | 2009-06-10 | 中国科学院金属研究所 | Heat treating method of carbon graphite material |
| CN101997110A (en) * | 2009-08-19 | 2011-03-30 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing stannum-carbon composite cathode material for lithium ion battery by utilizing thermal carbon reduction method |
| CN103066243A (en) * | 2012-12-06 | 2013-04-24 | 中南大学 | Coke powder-based cathode material of lithium ion power battery and preparation method thereof |
| KR20160068566A (en) * | 2014-12-05 | 2016-06-15 | 주식회사 포스코 | Method and apparatus for producing binder for coke |
| CN105185997A (en) * | 2015-10-27 | 2015-12-23 | 中国科学院物理研究所 | Sodion secondary battery negative electrode material and preparing method and application thereof |
| CN106099124A (en) * | 2016-07-19 | 2016-11-09 | 辽宁科技大学 | A kind of preparation method of coal base hydrogen reduction carbon catalysis material |
| CN106229519A (en) * | 2016-07-29 | 2016-12-14 | 辽宁科技大学 | A kind of method utilizing coal to prepare auto-dope difunctional oxygen reaction eelctro-catalyst |
| CN107180958A (en) * | 2017-06-05 | 2017-09-19 | 三峡大学 | A kind of anthracite/silicon monoxide/amorphous carbon negative material and preparation method thereof |
| CN107342409A (en) * | 2017-06-29 | 2017-11-10 | 三峡大学 | A kind of high-performance anthracite/silicon monoxide/phosphorus composite negative pole material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115722224A (en) * | 2022-09-12 | 2023-03-03 | 遂宁碳基环保科技有限公司 | Carbon-supported transition metal catalyst for sewage treatment and preparation method and application thereof |
| CN115722224B (en) * | 2022-09-12 | 2023-05-23 | 遂宁碳基环保科技有限公司 | Carbon-supported transition metal catalyst for sewage treatment and preparation method and application thereof |
| CN115744896A (en) * | 2022-11-30 | 2023-03-07 | 湖南宸宇富基新能源科技有限公司 | Artificial graphite @ crystalline flake graphite @ amorphous carbon composite active material and preparation and application thereof |
| CN115744896B (en) * | 2022-11-30 | 2024-01-09 | 湖南宸宇富基新能源科技有限公司 | Artificial graphite @ crystalline graphite @ amorphous carbon composite active material, preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110061199B (en) | 2023-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104538595B (en) | Embedded nano metal load type carbon nano-sheet lithium ion battery negative material and its preparation method and application | |
| CN103165862B (en) | A kind of high performance lithium ionic cell cathode material and preparation method thereof | |
| CN107275606B (en) | Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof | |
| CN103811717B (en) | Lithium ion battery cathode material of nucleocapsid structure and preparation method thereof | |
| Ramachandran et al. | Electrochemical performance of plate-like zinc cobaltite electrode material for supercapacitor applications | |
| CN106169582B (en) | A kind of natural needle coke composite graphite negative electrode material production method | |
| Chen et al. | Graphene quantum dots modified nanoporous SiAl composite as an advanced anode for lithium storage | |
| CN102745663B (en) | Method for preparing lithium iron phosphate material | |
| Wen et al. | Carbon-encapsulated Bi2Te3 derived from metal-organic framework as anode for highly durable lithium and sodium storage | |
| CN106410164A (en) | High-performance composite material and preparation method and application thereof | |
| CN107732203B (en) | Preparation method of nano cerium dioxide/graphene/sulfur composite material | |
| CN108807892A (en) | A kind of preparation method of asphaltic base silicon-carbon nanometer sheet lithium cell negative pole material | |
| CN112117444A (en) | Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery | |
| CN108767203B (en) | Titanium dioxide nanotube-graphene-sulfur composite material and preparation method and application thereof | |
| CN110061199A (en) | A kind of composite negative pole material of metal-carbon and its preparation method and application | |
| CN103531789A (en) | Iron oxide-carbon nanotube ternary composite material and preparation method thereof | |
| Wang et al. | ZIF-67-derived porous nitrogen-doped carbon shell encapsulates photovoltaic silicon cutting waste as anode in high-performance lithium-ion batteries | |
| CN114604896A (en) | MXene composite modified binary manganese-based sodium electro-precursor and preparation method thereof | |
| Xiao et al. | Boron-doped porous waste silicon/carbon composite with improved performance for lithium-ion batteries | |
| CN110061197B (en) | Coal-based battery negative electrode material and preparation method and application thereof | |
| Cheng | Hierarchical MnCo2O4 micro/nano fibres as a high-performance anode of lithium-ion battery | |
| CN110061198B (en) | Silicon-carbon composite negative electrode material and preparation method and application thereof | |
| CN114804095B (en) | Graphite negative electrode active material prepared from spheroidized graphite micropowder waste, and preparation method and application thereof | |
| CN105977483A (en) | Carbon-based nanocomposite material for electrode | |
| CN102891293A (en) | Method for manufacturing anode composite material of lithium ion battery |
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 |