CN103915628B - A kind of preparation method of carbon composite anode - Google Patents
A kind of preparation method of carbon composite anode Download PDFInfo
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- CN103915628B CN103915628B CN201310004734.2A CN201310004734A CN103915628B CN 103915628 B CN103915628 B CN 103915628B CN 201310004734 A CN201310004734 A CN 201310004734A CN 103915628 B CN103915628 B CN 103915628B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000006258 conductive agent Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 229910021312 NaFePO4 Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910021225 NaCoO2 Inorganic materials 0.000 claims description 2
- 229910019330 NaMn2O4 Inorganic materials 0.000 claims description 2
- 229910019338 NaMnO2 Inorganic materials 0.000 claims description 2
- 229910019013 NaNiO2 Inorganic materials 0.000 claims description 2
- 229910019463 NaV2 Inorganic materials 0.000 claims description 2
- 239000004964 aerogel Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229940009493 gel-one Drugs 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 9
- 229910001415 sodium ion Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000004146 energy storage Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007832 Na2SO4 Substances 0.000 description 3
- 229910018095 Ni-MH Inorganic materials 0.000 description 3
- 229910018477 Ni—MH Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910001222 NaVPO4F Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- -1 phosphide Chemical compound 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of preparation method of carbon composite anode, and the carbonaceous material of mass ratio 1% 40% is added into the base material of inlaid scheme containing sodium.The present invention prepares carbon composite anode, with higher battery specific power, excellent cycle performance of battery by adding the preferable carbonaceous material of electric conductivity in the inlaid scheme containing sodium.
Description
Technical field
The present invention relates to a kind of preparation method of carbon composite anode, more particularly to a kind of carbon composite anode in sode cell field
Preparation method.
Background technology
With continuing to develop for society, the mankind are gradually increased to the degree of dependence of the energy.But, traditional energy is generally not
Regenerative resource, with the increase of exploitation usage amount, is being faced with the danger of exhaustion.In recent years, what some can regenerate is clear
The clean energy, such as nuclear energy, water energy, wind energy, solar energy are increasingly becoming the focus that various countries are studied.For wind energy, solar energy etc
The energy, the features such as usually fluctuating larger with scattered, energy supply are, it is necessary to a more reliable energy-storage system collocation, ability
Obtain more smoothly exporting.
At present, energy-storage system has water-storage, flywheel energy storage, compressed-air energy storage, superconducting energy storage, secondary cell and super
The diversified forms such as capacitor energy storage.Wherein, secondary cell and ultracapacitor energy storage have obtained widely should in daily life
With.Secondary cell specific energy is high, operating voltage is high；Ultracapacitor multiplying power and good cycle.Secondary cell and super simultaneously
Capacitor is there is also more clearly disadvantageous, for the bar such as the low cost of energy-storage system requirement, long-life, environment-friendly, safe
Part can not be fully met.
U.S. Patent application US20090253025A1 proposes a kind of aqueous Rechargeable battery based on sodium ion,
Its operation principle is similar to lithium ion battery, is realized by the reciprocating motion of " rocking chair " formula of sodium ion in charge and discharge process
Conversion between electric energy and chemical energy.The flat seminars of Fudan University Wu Yu it is also proposed this asymmetry water system sodium-ion battery
(Chinese patent application CN101241802A, CN101087018A), mainly uses the inlaid scheme containing sodium, activated carbon etc. for just
Negative material, obtains a kind of new rechargeable battery.
At present, the research of sodium-ion battery is just in the starting stage.It is poor in terms of high rate performance, thus need one badly
The specific power of battery can be improved by planting, and improve the sodium-ion battery positive material preparation method of cycle performance.
The content of the invention
Present invention aims at a kind of preparation method of sodium-ion battery carbon composite anode, the present invention is by containing the embedding of sodium
Enter the addition preferable carbonaceous material of electric conductivity in compound, prepare carbon composite anode, it is excellent with higher battery specific power
Cycle performance of battery.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of carbon composite anode, comprises the following steps：
1) the grinding sieving of sodium inlaid scheme base material will be contained；
2) to step 1) described in grinding sieving after base material in add mass ratio 1%-40% carbonaceous material and solvent
Afterwards, regrind, form slurry；
3) mass ratio 5%-20% binding agent is dissolved in solvent, adds conductive agent and step of the mass ratio for 1%-20%
It is rapid 2) described in slurry, it is scattered at a high speed using cut mode, form living solution；
4) heating evaporation step 3) described in living solution, be made active material；
5) by step 4) described in active material by including kneading, limit diaphragm is made in the process of roll-in；
6) by step 5) described in membrane cutting after, be pressed on suitable size collector, prepare positive plate.
Step 1) described in the base material of inlaid scheme containing sodium be transition metal oxide, sulfide, phosphide, sulfuric acid
The sodium salt base material of salt, phosphate or doping metals or halogen.
Step 1) described in the base material of inlaid scheme containing sodium can include NaMn2O4、NaMnO2、NaCoO2、NaNiO2、
NaFePO4、NaFePO4F、NaV2O5Or NaVPO4F one or more；Be additionally may included in aforementioned substrates be doped with K, Mg,
The base material of one or more of elements in Al, Cu, Mn, Ti, Zn or F.
Step 2) described in carbonaceous material can include activated carbon, mesoporous carbon, CNT, carbon nanocoils, graphene,
It is one or more of in vitrescence carbon, carbon fiber or charcoal-aero gel.
Step 3) described in solvent can be one or more in ethanol, propyl alcohol, normal propyl alcohol, isopropanol or butanol.
Step 3) described in blend step can be using cut mode scattered, mechanical agitation, magnetic agitation or ball at a high speed
The mode of mill.
Step 4) described in solvent can be one or more in ethanol, propyl alcohol, normal propyl alcohol, isopropanol or butanol.
Carbon composite anode prepared by the preparation method of described carbon composite anode, the mass ratio of the carbonaceous material is 1%-
40%.
The present invention proposes the method for modifying of a kind of sodium-ion battery positive material and positive pole, prepares sodium-ion battery carbon and answers
Positive pole is closed, the positive pole prepared using the method for the present invention can be used for aqueous sodium-ion battery.Compared with the existing technology, it has
Higher specific discharge capacity and electric discharge specific energy, can greatly improve the multiplying power and cycle performance of battery.Further, it is also possible to improve
The processing characteristics of positive pole, improves the hydrophily of electrode slice, is conducive to electrolyte sufficiently to infiltrate.
Embodiment
Below by embodiment, technical scheme is described in further detail, but is not limited to embodiment
Content.
Embodiment 1
Using the NaMnO of the grinding sieving of mass ratio 75%2Base material, the activated carbon of mass ratio 25% and ethanol mixing are equal
Even, regrinding forms slurry；According to slurry：Conductive agent：Binding agent=80:10:10, i.e. slurry 80%, conductive agent 10% glue
The mass ratio and solvent for tying agent 10% are tuned into living solution, are sufficiently mixed using high speed shear mode；Activity is evaporated at 45 DEG C
Solution is made active material, then through kneading, the step such as roll the limit diaphragm that thickness is 200 μm be made.It is cut into φ 12mm circle
Piece, is pressed in the foamed nickel current collector of suitable size, dries, weighs, positive plate is made.
GND preparation process is identical with positive pole, negative electrode active material：Conductive agent：Binding agent=80:10:10.According to
Both positive and negative polarity mass ratio 1.2:1 pairing, in 0.5mol/L Na2SO4Vacuum impregnation 4h in the aqueous solution, using commercial Ni-MH battery without
It is that barrier film is assembled into button cell to spin cloth.Battery high rate performance test is carried out after standing overnight.Using constant current charge-discharge, voltage model
Enclose 0.2V-1.85V.
Battery is with 0.3C rate charge-discharge, and specific energy is 27Wh/kg；With 1C rate charge-discharge, specific energy is
20.1Wh/kg, 500 specific energies of circulation are substantially undamped.
Embodiment 2
Using the NaMnO of the grinding sieving of mass ratio 99%2Base material, the CNT of mass ratio 1% and propyl alcohol mixing
Uniformly, regrinding forms slurry；According to slurry：Conductive agent：Binding agent=75:5:20, i.e. slurry 75%, conductive agent 5% glue
The mass ratio and solvent for tying agent 20% are tuned into living solution, are mixed using mechanical agitation；Living solution is evaporated at 45 DEG C to be made
Active material, then through kneading, the step such as roll the limit diaphragm that thickness is 210 μm be made.φ 15mm disk is cut into, is pressed in suitable
In the foamed nickel current collector of suitable size, dry, weigh, positive plate is made.
GND preparation process is identical with positive pole, negative electrode active material：Conductive agent：Binding agent=80:10:10.According to
Both positive and negative polarity mass ratio 1.2:1 pairing, in 0.5mol/L Na2SO4Vacuum impregnation 4h in the aqueous solution, using commercial Ni-MH battery without
It is that barrier film is assembled into button cell to spin cloth.Battery high rate performance test is carried out after standing overnight.Using constant current charge-discharge, voltage model
Enclose 0.2V-1.85V.
Battery is with 0.3C rate charge-discharge, and specific energy is 28.9Wh/kg；Battery is with 1C rate charge-discharge, specific energy
It is substantially undamped that 500 specific energies are circulated for 22.2Wh/kg.
Embodiment 3
Using the NaMnO of the grinding sieving of mass ratio 60%2Base material, the mesoporous carbon of mass ratio 40% and isopropanol mixing
Uniformly, regrinding forms slurry；According to slurry：Conductive agent：Binding agent=79:20:1, i.e. slurry 79%, conductive agent 20%,
The mass ratio of binding agent 1% is tuned into living solution with solvent, is sufficiently mixed using ball milling method；Living solution is evaporated at 45 DEG C
Be made active material, then through kneading, the step such as roll the limit diaphragm that thickness is 250 μm be made.φ 10mm disk is cut into, is pressed
In the foamed nickel current collector of suitable size, dry, weigh, positive plate is made.
GND preparation process is identical with positive pole, negative electrode active material：Conductive agent：Binding agent=80:10:10.According to
Both positive and negative polarity mass ratio 1.2:1 pairing, in 0.5mol/L Na2SO4Vacuum impregnation 4h in the aqueous solution, using commercial Ni-MH battery without
It is that barrier film is assembled into button cell to spin cloth.Battery high rate performance test is carried out after standing overnight.Using constant current charge-discharge, voltage model
Enclose 0.2V-1.85V.
Battery is with 0.3C rate charge-discharge, and specific energy is 27.6Wh/kg；Battery is with 1C rate charge-discharge, specific energy
For 20.4Wh/kg；Circulate 500 specific energies substantially undamped.
Comparative example 1
The content of comparative example 1 is as different from Example 1：Using the NaMnO of the grinding sieving of mass ratio 100%2Base material with
Ethanol is well mixed.
Battery is with 0.3C rate charge-discharge, and specific energy is 23.77Wh/kg；With 1C rate charge-discharge, specific energy is
18.1Wh/kg, circulates 500 specific energy conservation rates 98%.
It is compound with carbon in embodiment 1-3 in the case of negative pole identical it was found from comparative example 1 and embodiment 1-3 comparison
The battery specific energy of battery prepared by positive pole with the specific energy of the rate charge-discharge of 0.3C1C sums better than comparative example 1 with the conditions of；
500 specific energies are circulated in embodiment 1-3 substantially undamped, the energy conservation rate 98% of comparative example 1, embodiment 1-3 cyclicity
Comparative example 1 can be better than.
Claims (9)
1. a kind of preparation method of carbon composite anode, it is characterised in that comprise the following steps：
1) the grinding sieving of sodium inlaid scheme base material will be contained, the base material of inlaid scheme containing sodium is transition metal oxide
Sodium salt base material or NaFePO4Base material；
2) to step 1) described in grinding sieving after base material in add after mass ratio 1%-40% carbonaceous material and solvent, enter
Row regrinding, forms slurry, and wherein mass ratio refers to the quality of carbonaceous material and step 1) described in grinding sieving after base
The ratio of the gross mass of material and carbonaceous material；
3) mass ratio 5%-20% binding agent is dissolved in solvent, adds conductive agent and step 2 of the mass ratio for 1%-20%)
Described slurry mixing, forms living solution, and wherein mass ratio refers to the quality and binding agent, conductive agent of binding agent or conductive agent
And step 2) described in slurry gross mass ratio；
4) heating evaporation step 3) described in living solution, be made active material；
5) by step 4) described in active material by including kneading, limit diaphragm is made in the process of roll-in；
6) by step 5) described in membrane cutting after, be pressed on suitable size collector, prepare positive plate.
2. the preparation method of carbon composite anode according to claim 1, it is characterised in that step 1) described in it is embedding containing sodium
Enter the sodium salt base material that compound substrate is the transition metal oxide for being doped with metal or halogen, or to be doped with metal
Or the NaFePO of halogen4Base material.
3. the preparation method of carbon composite anode according to claim 1, it is characterised in that step 1) described in transition gold
Belonging to the sodium salt base material of oxide includes NaMn2O4、NaMnO2、NaCoO2、NaNiO2Or NaV2O5One or more.
4. the preparation method of carbon composite anode according to claim 2, it is characterised in that the metallic element include K, Mg,
Al、Cu、Mn、Ti、Zn；The halogen includes F.
5. the preparation method of carbon composite anode according to claim 1, it is characterised in that step 2) described in carbonaceous material
Material include in activated carbon, mesoporous carbon, CNT, carbon nanocoils, graphene, vitrescence carbon, carbon fiber or charcoal-aero gel one kind or
It is several.
6. the preparation method of carbon composite anode according to claim 1, it is characterised in that step 3) described in solvent be
One or more in ethanol, propyl alcohol, normal propyl alcohol, isopropanol or butanol.
7. the preparation method of carbon composite anode according to claim 1, it is characterised in that step 3) described in mixing step
It is rapid to be disperseed at a high speed using cut mode, by the way of mechanical agitation, magnetic agitation or ball milling.
8. the preparation method of carbon composite anode according to claim 1, it is characterised in that step 2) described in solvent be
One or more in ethanol, propyl alcohol, normal propyl alcohol, isopropanol or butanol.
9. carbon composite anode prepared by the preparation method of the carbon composite anode according to any one in claim 1-8, its
The mass ratio for being characterised by the carbonaceous material is 1%-40%, and wherein mass ratio refers to the quality and step 1 of carbonaceous material) institute
The ratio of the gross mass of base material and carbonaceous material after the grinding sieving stated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310004734.2A CN103915628B (en) | 2013-01-06 | 2013-01-06 | A kind of preparation method of carbon composite anode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310004734.2A CN103915628B (en) | 2013-01-06 | 2013-01-06 | A kind of preparation method of carbon composite anode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103915628A CN103915628A (en) | 2014-07-09 |
| CN103915628B true CN103915628B (en) | 2017-09-12 |
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| CN102569797B (en) * | 2012-01-20 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Novel phosphate based composite cathode material, its preparation method and application thereof |
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