CN104362336B - A kind of original position prepares the method for Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material - Google Patents
A kind of original position prepares the method for Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material Download PDFInfo
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- 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
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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- 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
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- 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
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Abstract
A kind of original position prepares the method for Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material, the present invention relates to the preparation of inorganic nano composite material.The invention solves the problems that in the preparation process of existing Cobalto-cobaltic oxide graphene composite material or there is material disperses uneven, or there is physical property decline in Graphene oxidation-reduction process, and manufacturing cycle is long, the problem that process is complicated.Method: one, mixing;Two, ball milling;Three, hydro-thermal reaction;Four, heat treatment, i.e. obtains Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material.The present invention is for preparing Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material in situ.
Description
Technical field
The present invention relates to the preparation of inorganic nano composite material.
Background technology
In lithium-ion battery system, electrode material cost occupies absolute specific gravity, therefore seeks low cost, high capacity density and peace
The lithium ion battery electrode material system that loopful is protected is the emphasis of domestic and international Study on Li-ion batteries.In commercial lithium-ion batteries
Graphite negative electrodes material is widely used, but its theoretical capacity is only 372mAh/g.Tarascon in 2000 etc. are at Nature
Proposing transition metal oxide Co3O4 in magazine first can be negative material, it is advantageous that theoretical capacity is high, the most forthright
Energy is good and safety is high, and abundant raw material source, environmental friendliness, is the most potential negative material.But, Co3O4
During the embedding lithium of negative material/de-lithium, change in volume is violent, shows as cycle performance difference or negative material lost efficacy.Four oxidations three
Cobalt nanorize and Cobalto-cobaltic oxide class composite negative pole material are the effective ways solving the problems referred to above.
Advantage based on cobaltic-cobaltous oxide negative pole material, in conjunction with Graphene brilliance chemical stability, electrical conductivity, very big specific surface
Long-pending feature, New Co 3O4/ graphene composite negative pole has obtained paying close attention to widely.At present, have been provided for both at home and abroad
The method of a series of preparation cobalt oxide/graphene composite negative pole materials.As (1) ZL 201010158087.7 provides one
Plant graphene-supported cobaltosic oxide nano composite material, first graphene oxide solution and divalent cobalt etc. are mixed, then
Mixing in ultrasonic addition pyroreaction still and anneal 3~30 hours at 100~250 DEG C, scrubbed dry acquisition Graphene is born
Carry cobaltosic oxide nano composite material.(2) CN201210305493 provides a kind of Cobalto-cobaltic oxide-Graphene composite wood
The preparation method of material, first prepares graphene oxide suspension, is subsequently adding cobalt hydroxide and obtains the two mixture, protectiveness
Lower 500 DEG C~700 DEG C of atmosphere processes 0.5h~2h, it is thus achieved that Cobalto-cobaltic oxide-graphene composite material.But method exists at present
Two significant shortcomings: one is often to use first to prepare Graphene, the method then carrying out Cobalto-cobaltic oxide load, cause multiple
In condensation material, the two dispersion is the most uniform;Two is that widely used Hummers method prepares Graphene, but graphite in oxidizing process
Alkene shows to introduce a large amount of organo-functional group (hydroxyl, carboxyl, epoxy and carbonyl), but it cannot be removed by reduction process completely,
And oxidizing process causes graphite platelet structure to be destroyed, defect increases, and causes physical property to reduce: reduced by graphene oxide
Its electrical conductivity rear can produce the raising of 4 orders of magnitude, but the graphene oxide electrical conductivity of reduction still is below Graphene
10-100 times, and oxidation-reduction method manufacturing cycle length (8~48h), process is complicated and expensive, limits it and extensively should
With.
Summary of the invention
The invention solves the problems that in the preparation process of existing Cobalto-cobaltic oxide-graphene composite material or there is material dispersion inequality
Even, or there is physical property decline in Graphene oxidation-reduction process, manufacturing cycle is long, the problem that process is complicated, and
A kind of method that original position prepares Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material is provided.
A kind of original position prepares the method for Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material, specifically according to following
Step is carried out:
One, mixing: by expanded graphite, carbon-based compound, decomposes can go out material and the Cobalto-cobaltic oxide of hydroxide ion
Presoma joins and dissolves mixing in the water containing acetic acid, obtains mixed liquor;
Described expanded graphite is (0.1~0.5) with the mass ratio of cobaltosic oxide precursor: 1;Described carbon-based compound and four
The mass ratio of Co 3 O presoma is (0.2~1.0): 1;Described decomposes can go out material and four oxidations of hydroxide ion
The mol ratio of three cobalt precursor is (2~8): 1;The volume of described water with the mass ratio of cobaltosic oxide precursor is
(50~200) mL:1g;Described acetic acid is (0.01~0.04) with the volume ratio of water: 1;
Two, ball milling: mixed liquor is placed in planetary ball mill, ball milling 4h~24h under rotating speed is 200r/min~400r/min,
Obtain dispersion liquid in situ;
Three, hydro-thermal reaction: be placed in teflon-lined reactor by original position dispersion liquid, is 160 DEG C~190 in temperature
Hydro-thermal reaction 2h~10h at DEG C, obtain the liquid after hydro-thermal reaction;
Four, heat treatment: be centrifuged being dried by the liquid after hydro-thermal reaction, is then 350 DEG C~500 at inert atmosphere and temperature
Heat treatment 0.5h~2h at DEG C, i.e. obtains Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material.
The invention has the beneficial effects as follows: Cobalto-cobaltic oxide/charcoal/graphite nanosheets nano composite material excellent that the present invention provides
It is in place of gesture: (1) uses physics to peel off graphite microchip, and the graphite nanosheets defect of preparation is few, and lamellar structure is complete,
Maintain the original performance of graphite;(2) by expanded graphite, carbon-based compound, can decomposes go out hydroxide ion material,
Cobaltosic oxide precursor prepares compound dispersing agent in proportion in situ, the stripping of graphite flake layer, stone in this original position preparation process
The dispersion of ink sheet layer, the load of cobaltosic oxide precursor synchronize to realize;(3) In-situ reaction dispersion carries out hydro-thermal reaction
Preparation nano composite material, generation, the in-situ reducing of graphite flake layer that in hydrothermal reaction process, cobaltosic oxide nano is brilliant, receives
The generation of nano composite material synchronizes to realize;(4) preparation process adds carbon-based compound in situ as dispersant, its organic official
The uniformity that ensure that suspension in situ can be rolled into a ball, and then ensure that the uniformity preparing composite in situ, hydrothermal treatment consists simultaneously
Rear carbon-based compound is changed into charcoal, is coated on cobaltosic oxide precursor surface, it is ensured that prepared Cobalto-cobaltic oxide is nanometer
Grade particles.
In complex prepared by the present invention, graphite nanosheets is uniformly dispersed, and Cobalto-cobaltic oxide Load Balanced is firm, the most in situ
Dispersant hydro-thermal carbonization in preparation process, it is achieved the system of Cobalto-cobaltic oxide/charcoal/graphite nanosheets nano composite anode material
Standby.Cobalto-cobaltic oxide/charcoal prepared by the present invention/graphite nanosheets composite negative pole material first charge-discharge capacity up to
816mAh/g, preparation method is simple, manufacturing cycle short (6-10h), it is not necessary to expensive equipment, favorable reproducibility, is also not required to
Want complicated chemical treating process, be suitable for large-scale production, there is good application prospect.
A kind of method that the present invention prepares Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material for original position.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material of embodiment one preparation;
1 is Cobalto-cobaltic oxide, and 2 is graphite nanosheets;
Fig. 2 is the cycle performance curve of the Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material of embodiment two preparation;
Fig. 3 is the scanning electron microscope (SEM) photograph of the Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material of embodiment three preparation.
Detailed description of the invention
Technical solution of the present invention is not limited to the detailed description of the invention of act set forth below, also includes between each detailed description of the invention
Combination in any.
Detailed description of the invention one: a kind of Cobalto-cobaltic oxide/charcoal/graphite nanosheets of preparing in situ described in present embodiment is combined
The method of negative material, specifically follows the steps below:
One, mixing: by expanded graphite, carbon-based compound, decomposes can go out material and the Cobalto-cobaltic oxide of hydroxide ion
Presoma joins and dissolves mixing in the water containing acetic acid, obtains mixed liquor;
Described expanded graphite is (0.1~0.5) with the mass ratio of cobaltosic oxide precursor: 1;Described carbon-based compound and four
The mass ratio of Co 3 O presoma is (0.2~1.0): 1;Described decomposes can go out material and four oxidations of hydroxide ion
The mol ratio of three cobalt precursor is (2~8): 1;The volume of described water with the mass ratio of cobaltosic oxide precursor is
(50~200) mL:1g;Described acetic acid is (0.01~0.04) with the volume ratio of water: 1;
Two, ball milling: mixed liquor is placed in planetary ball mill, ball milling 4h~24h under rotating speed is 200r/min~400r/min,
Obtain dispersion liquid in situ;
Three, hydro-thermal reaction: be placed in teflon-lined reactor by original position dispersion liquid, is 160 DEG C~190 in temperature
Hydro-thermal reaction 2h~10h at DEG C, obtain the liquid after hydro-thermal reaction;
Four, heat treatment: be centrifuged being dried by the liquid after hydro-thermal reaction, is then 350 DEG C~500 at inert atmosphere and temperature
Heat treatment 0.5h~2h at DEG C, i.e. obtains Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material.
Present embodiment provides the benefit that: Cobalto-cobaltic oxide/charcoal/graphite nanosheets that present embodiment provides is nano combined
Being advantageous in that of material: (1) uses physics to peel off graphite microchip, and the graphite nanosheets defect of preparation is few, and lamella is tied
Structure is complete, maintains the original performance of graphite;(2) by expanded graphite, carbon-based compound, can decomposes go out hydroxyl from
The material of son, cobaltosic oxide precursor prepare compound dispersing agent in proportion in situ, graphite flake layer in this original position preparation process
Stripping, the dispersion of graphite flake layer, cobaltosic oxide precursor load synchronize realize;(3) In-situ reaction dispersion enters
Row hydro-thermal reaction prepares nano composite material, generation that in hydrothermal reaction process, cobaltosic oxide nano is brilliant, graphite flake layer former
Position reduction, the generation of nano composite material synchronize to realize;(4) preparation process adds carbon-based compound in situ as dispersant,
Its organo-functional group ensure that the uniformity of suspension in situ, and then ensure that the uniformity preparing composite in situ, simultaneously
After hydrothermal treatment consists, carbon-based compound is changed into charcoal, is coated on cobaltosic oxide precursor surface, it is ensured that prepared four oxidations three
Cobalt is nano-scale particle.
In complex prepared by present embodiment, graphite nanosheets is uniformly dispersed, and Cobalto-cobaltic oxide Load Balanced is firm, simultaneously
Dispersant hydro-thermal carbonization in preparation process in situ, it is achieved Cobalto-cobaltic oxide/charcoal/graphite nanosheets nano composite anode material
Preparation.Cobalto-cobaltic oxide/charcoal prepared by present embodiment/graphite nanosheets composite negative pole material first charge-discharge capacity up to
816mAh/g, preparation method is simple, manufacturing cycle short (6-10h), it is not necessary to expensive equipment, favorable reproducibility, is also not required to
Want complicated chemical treating process, be suitable for large-scale production, there is good application prospect.
Detailed description of the invention two: present embodiment is unlike detailed description of the invention one: the charcoal base described in step one
Compound is a kind of or the most several mixture in chitosan, carboxymethyl chitosan and water-soluble chitosan.Other with tool
Body embodiment one is identical.
Detailed description of the invention three: present embodiment is unlike one of detailed description of the invention one or two: in step one
Described can decomposes to go out the material of hydroxide ion be the one in carbamide, aminoquinoxaline, ammonium cyanate, ammonium thiocyanate
Or the most several mixture.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment is unlike one of detailed description of the invention one to three: in step one
Described cobaltosic oxide precursor is a kind of or the most several mixture in cobalt nitrate, cobaltous chloride and cobalt oxalate.Other
Identical with detailed description of the invention one to three.
Detailed description of the invention five: present embodiment is unlike one of detailed description of the invention one to four: in step one
Described expanded graphite is (0.1~0.3) with the mass ratio of cobaltosic oxide precursor: 1.Other is with detailed description of the invention one to four
Identical.
Detailed description of the invention six: present embodiment is unlike one of detailed description of the invention one to five: in step one
Described carbon-based compound is (0.2~0.4) with the mass ratio of cobaltosic oxide precursor: 1.Other with detailed description of the invention one to
Five is identical.
Detailed description of the invention seven: present embodiment is unlike one of detailed description of the invention one to six: in step one
Described can the mol ratio of the decomposes material and cobaltosic oxide precursor that go out hydroxide ion be (3~6): 1.Other with tool
Body embodiment one to six is identical.
Detailed description of the invention eight: present embodiment is unlike one of detailed description of the invention one to seven: in step one
The volume of described water and the mass ratio of cobaltosic oxide precursor are (100~150) mL:1g.Other is with detailed description of the invention one
Identical to seven.
Detailed description of the invention nine: present embodiment is unlike one of detailed description of the invention one to eight: in step one
Described acetic acid is (0.01~0.02) with the volume ratio of water: 1.Other is identical with detailed description of the invention one to eight.
Detailed description of the invention ten: present embodiment is unlike one of detailed description of the invention one to nine: in step 4
Heat treatment 0.5h~1h at inert atmosphere and temperature are 400 DEG C~500 DEG C.Other is identical with detailed description of the invention one to nine.
Employing following example checking beneficial effects of the present invention:
Embodiment one:
A kind of original position described in the present embodiment prepares the method for Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material, tool
Body follows the steps below:
One, by chitosan, 2.0g carbamide and 1.14g cobalt nitrate that 0.2g expanded graphite, 0.2g mean molecule quantity are 6.5 ten thousand
Join and the water containing acetic acid dissolves mixing, obtain mixed liquor;Described acetic acid is 1mL, and described water is 100mL;
Two, mixed liquor is placed in planetary ball mill, ball milling 12h under rotating speed is 350r/min, obtains dispersion liquid in situ;
Three, original position dispersion liquid is placed in teflon-lined reactor, hydro-thermal reaction 4h at temperature is 160 DEG C,
Obtain the liquid after hydro-thermal reaction;
Four, it is centrifuged being dried by the liquid after hydro-thermal reaction, is then heat treatment at 450 DEG C at inert atmosphere and temperature
0.5h, i.e. obtains Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material.
Cobalto-cobaltic oxide, charcoal, nanometer in Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material prepared by the present embodiment
The mass ratio of graphite microchip is 1:0.1:0.4.
Fig. 1 is the X-ray diffractogram of the Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material of embodiment one preparation,
1 is Cobalto-cobaltic oxide, and 2 is graphite nanosheets;As seen from the figure, the spy of Cobalto-cobaltic oxide, graphite nanosheets is occurred in that
Levy diffraction maximum, show to achieve the preparation of composite.Owing in composite, charcoal is amorphous state, and content is relatively low,
Therefore inconspicuous in X-ray diffractogram, use thermogravimetric analysis to can determine that carbon content in composite.
It is as follows that Cobalto-cobaltic oxide/charcoal prepared by the present embodiment/graphite nanosheets composite negative pole material assembles half-cell step: will
Composite negative pole material, binding agent, acetylene carbon black three are that 80:10:10 carries out 1h mixing and uniformly coats according to mass ratio
On Copper Foil, it is then that 120 DEG C of dry 8h obtain negative poles in temperature, with metal lithium sheet for electrode, by lithium hexafluoro phosphate
It is dissolved in the mixed liquor of ethylene carbonate/diethyl carbonate that volume ratio is 1:1 and obtains electrolyte, in described electrolyte
The concentration of lithium hexafluoro phosphate is 1mol/L, then uses the capacity of Land battery test system test compound negative material, warp
Test show that composite negative pole material first charge-discharge capacity has reached 816mAh/g, and after 50 discharge and recharges, capacity still keeps
At 679mAh/g.
Embodiment two:
A kind of original position described in the present embodiment prepares the method for Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material, tool
Body follows the steps below:
One, by chitosan, 6.0g carbamide and 1.62g cobaltous chloride that 0.1g expanded graphite, 0.2g mean molecule quantity are 3.4 ten thousand
Join and the water containing acetic acid dissolves mixing, obtain mixed liquor;Described acetic acid is 1mL, and described water is 100mL;
Two, mixed liquor is placed in planetary ball mill, ball milling 24h under rotating speed is 300r/min, obtains dispersion liquid in situ;
Three, original position dispersion liquid is placed in teflon-lined reactor, hydro-thermal reaction 2h at temperature is 180 DEG C,
Obtain the liquid after hydro-thermal reaction;
Four, it is centrifuged being dried by the liquid after hydro-thermal reaction, is then heat treatment 1h at 400 DEG C at inert atmosphere and temperature,
I.e. obtain Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material.
Cobalto-cobaltic oxide, charcoal, nanometer in the Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material of embodiment two preparation
The mass ratio of graphite microchip is 1:0.05:0.1.
Fig. 2 is the cycle performance curve of the Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material of embodiment two preparation.
It is as follows that Cobalto-cobaltic oxide/charcoal prepared by the present embodiment/graphite nanosheets composite negative pole material assembles half-cell step: will be compound
Negative material, binding agent, acetylene carbon black three are that 80:10:10 carries out 1h mixing and is coated uniformly on copper according to mass ratio
On paper tinsel, it is then that 120 DEG C of dry 8h obtain negative poles in temperature, with metal lithium sheet for electrode, by lithium hexafluoro phosphate dissolving
Electrolyte, hexafluoro in described electrolyte is obtained in the mixed liquor of ethylene carbonate/diethyl carbonate that volume ratio is 1:1
The concentration of lithium phosphate is 1mol/L, then uses the capacity of Land battery test system test compound negative material, after tested
Showing that composite negative pole material first charge-discharge capacity has reached 780mAh/g, after 40 discharge and recharges, capacity remains at
637mAh/g。
Embodiment three:
A kind of original position described in the present embodiment prepares the method for Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material, tool
Body follows the steps below:
One, 0.5g expanded graphite, 0.4g carboxymethyl chitosan, 3.0g carbamide and 1.83g cobalt oxalate are joined containing acetic acid
Water in dissolve mixing, obtain mixed liquor;Described acetic acid is 1mL, and described water is 100mL;
Two, mixed liquor is placed in planetary ball mill, ball milling 4h under rotating speed is 340r/min, obtains dispersion liquid in situ;
Three, original position dispersion liquid is placed in teflon-lined reactor, hydro-thermal reaction 3h at temperature is 160 DEG C,
Obtain the liquid after hydro-thermal reaction;
Four, it is centrifuged being dried by the liquid after hydro-thermal reaction, is then heat treatment at 450 DEG C at inert atmosphere and temperature
0.5h, i.e. obtains Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material.
Cobalto-cobaltic oxide, charcoal, nanometer in the Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material of embodiment three preparation
The mass ratio of graphite microchip is 1:0.2:1.
Fig. 3 is the scanning electron microscope (SEM) photograph of the Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material of embodiment three preparation, by
Figure understands, and in figure, sheet is graphite nanosheets, and graphite nanosheets shows four oxidations three that particulate material is charcoal cladding
Cobalt granule, it is seen that Cobalto-cobaltic oxide granule uniform load is on graphite nanosheets lamella.
It is as follows that Cobalto-cobaltic oxide/charcoal prepared by the present embodiment/graphite nanosheets composite negative pole material assembles half-cell step: will
Composite negative pole material, binding agent, acetylene carbon black three are that 80:10:10 carries out 1h mixing and uniformly coats according to mass ratio
On Copper Foil, it is then that 120 DEG C of dry 8h obtain negative poles in temperature, with metal lithium sheet for electrode, by lithium hexafluoro phosphate
It is dissolved in the mixed liquor of ethylene carbonate/diethyl carbonate that volume ratio is 1:1 and obtains electrolyte, in described electrolyte
The concentration of lithium hexafluoro phosphate is 1mol/L, then uses the capacity of Land battery test system test compound negative material, first
Secondary charge/discharge capacity has reached 679mAh/g, and after 100 discharge and recharges, capacity remains at 498mAh/g.
Claims (8)
1. the method that an original position prepares Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material, it is characterised in that a kind of
The method preparing Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material in situ follows the steps below:
One, mixing: by expanded graphite, carbon-based compound, decomposes can go out material and the Cobalto-cobaltic oxide of hydroxide ion
Presoma joins and dissolves mixing in the water containing acetic acid, obtains mixed liquor;
Described expanded graphite is (0.1~0.5) with the mass ratio of cobaltosic oxide precursor: 1;Described carbon-based compound and four oxygen
The mass ratio changing three cobalt precursor is (0.2~1.0): 1;Described decomposes can go out material and the Cobalto-cobaltic oxide of hydroxide ion
The mol ratio of presoma is (2~8): 1;The volume of described water with the mass ratio of cobaltosic oxide precursor is
(50~200) mL:1g;Described acetic acid is (0.01~0.04) with the volume ratio of water: 1;
Two, ball milling: mixed liquor is placed in planetary ball mill, ball milling 4h~24h under rotating speed is 200r/min~400r/min,
Obtain dispersion liquid in situ;
Three, hydro-thermal reaction: be placed in teflon-lined reactor by original position dispersion liquid, is 160 DEG C~190 in temperature
Hydro-thermal reaction 2h~10h at DEG C, obtain the liquid after hydro-thermal reaction;
Four, heat treatment: be centrifuged being dried by the liquid after hydro-thermal reaction, is then 350 DEG C~500 at inert atmosphere and temperature
Heat treatment 0.5h~2h at DEG C, i.e. obtains Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material;
Carbon-based compound described in step one is the one in chitosan, carboxymethyl chitosan and water-soluble chitosan or wherein
Several mixture;
Described in step one can decomposes to go out the material of hydroxide ion be carbamide, aminoquinoxaline, ammonium cyanate and sulfur cyanogen
A kind of or the most several mixture in acid ammonium.
A kind of original position the most according to claim 1 prepares Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material
Method, it is characterised in that the cobaltosic oxide precursor described in step one is in cobalt nitrate, cobaltous chloride and cobalt oxalate
Kind or the most several mixture.
A kind of original position the most according to claim 1 prepares Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material
Method, it is characterised in that the mass ratio of the expanded graphite described in step one and cobaltosic oxide precursor is (0.1~0.3): 1.
A kind of original position the most according to claim 1 prepares Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material
Method, it is characterised in that the carbon-based compound described in step one with the mass ratio of cobaltosic oxide precursor is
(0.2~0.4): 1.
A kind of original position the most according to claim 1 prepares Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material
Method, it is characterised in that decomposes can go out material and the cobaltosic oxide precursor of hydroxide ion described in step one
Mol ratio be (3~6): 1.
A kind of original position the most according to claim 1 prepares Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material
Method, it is characterised in that the volume of the water described in step one with the mass ratio of cobaltosic oxide precursor is
(100~150) mL:1g.
A kind of original position the most according to claim 1 prepares Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material
Method, it is characterised in that the volume ratio of the acetic acid described in step one and water is (0.01~0.02): 1.
A kind of original position the most according to claim 1 prepares Cobalto-cobaltic oxide/charcoal/graphite nanosheets composite negative pole material
Method, it is characterised in that in step 4 at inert atmosphere and temperature are 400 DEG C~500 DEG C heat treatment 0.5h~1h.
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