CN103887489B - A kind of preparation method of height ratio capacity graphene coated nickel-cobalt lithium manganate material - Google Patents
A kind of preparation method of height ratio capacity graphene coated nickel-cobalt lithium manganate material Download PDFInfo
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- CN103887489B CN103887489B CN201310739997.8A CN201310739997A CN103887489B CN 103887489 B CN103887489 B CN 103887489B CN 201310739997 A CN201310739997 A CN 201310739997A CN 103887489 B CN103887489 B CN 103887489B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 91
- 239000000463 material Substances 0.000 title claims abstract description 77
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 55
- 229910002804 graphite Inorganic materials 0.000 claims description 51
- 239000010439 graphite Substances 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910003900 Li(Ni0.5Co0.2Mn0.3)O2 Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 238000005476 soldering Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910004493 Li(Ni1/3Co1/3Mn1/3)O2 Inorganic materials 0.000 claims description 2
- 229910016482 Ni0.4Co0.2Mn0.4 Inorganic materials 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 238000010494 dissociation reaction Methods 0.000 claims description 2
- 230000005593 dissociations Effects 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims 2
- 238000005253 cladding Methods 0.000 claims 1
- -1 graphite Alkene Chemical class 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052744 lithium Inorganic materials 0.000 abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 11
- 239000010405 anode material Substances 0.000 abstract description 9
- 238000001035 drying Methods 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 5
- PAMMESUSQVJOMA-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O.[Ni].[Co] Chemical compound [Li].[Mn](=O)(=O)(O)O.[Ni].[Co] PAMMESUSQVJOMA-UHFFFAOYSA-L 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007787 solid Substances 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
- H01M4/48—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- 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
-
- 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of anode material for lithium-ion batteries, especially relate to the preparation method of a kind of height ratio capacity graphene coated nickel-cobalt lithium manganate material.Its specific discharge capacity being mainly solution nickle cobalt lithium manganate existing for prior art is relatively low, and nickelic nickle cobalt lithium manganate, nickel and lithium easily occur mixing phenomenon to cause the precipitation of lithium at material internal, when air humidity is bigger, and the technical problem that analysis lithium phenomenon the most seriously waits.The present invention uses nickel-cobalt lithium manganate material and graphene platelet, under the conditions of 180 DEG C, graphene platelet is dissolved in DMF solution and is configured to the Graphene DMF solution that concentration is 100 1000ppm, under conditions of stirring, DMF solution is added drop-wise in the nickel-cobalt lithium manganate material of preparation, above-mentioned resulting materials is put into 110 140 DEG C of drying in vacuum drying oven again, gets product.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries, especially relate to a kind of height ratio capacity graphene coated nickel cobalt
The preparation method of lithium manganate material.
Background technology
Lithium ion battery has been widely used for photographing unit, mobile phone, notebook computer etc. just as the energy of clean and effective
Take formula mobile device, and be gradually applied to electric automobile.Anode material for lithium-ion batteries is the portion of most critical in lithium ion battery
Point, exactly because many problems of positive electrode, limit some application of lithium ion battery.In order to make answering of lithium ion battery
With wider general, easier towards development of maximizing, improve positive electrode performance the most necessary.
The anode material for lithium-ion batteries of commercialization at present mainly has cobalt acid lithium, LiMn2O4, LiFePO 4 and nickel cobalt manganese
Acid lithium.Wherein, cobalt acid lithium is the positive electrode that market share is maximum, but cobalt resource is the most rare, expensive, and in mistake
There is potential safety hazard during charging, its application in high capacity cell receives the biggest restriction.Although the LiMn2O4 tool of stratiform
There is 200mAh g-1Specific capacity, but structural stability is very poor, and the LiMn2O4 specific capacity of spinel-type is the lowest, and high temperature
Under structural stability have to be strengthened.Ferrousphosphate lithium material tap density is low, poor processability, and limit this material enters one
Step application.Nickle cobalt lithium manganate uses relatively inexpensive nickel and manganese to instead of substantial amounts of cobalt in cobalt acid lithium, thus it is reducing cost
Aspect has obviously advantage；Meanwhile, its Stability Analysis of Structures, security performance is good, has higher electrical conductivity and heat stability.
Compare with other anode material for lithium-ion batteries, nickel-cobalt lithium manganate material and the chemical property of cobalt acid lithium material and processing characteristics
Closely, it is a kind of material most possibly replacing cobalt acid lithium, there is the biggest market prospect.
But although the specific discharge capacity that nickle cobalt lithium manganate has numerous advantage nickle cobalt lithium manganates is relatively low.Solve this at present
The method of problem is for putting forward high nickel content, but nickelic nickle cobalt lithium manganate, nickel and lithium easily occur mixing phenomenon to cause at material internal
The precipitation of lithium, when air humidity is bigger, analysis lithium phenomenon ratio is more serious.
Summary of the invention
The present invention is to provide the preparation method of a kind of height ratio capacity graphene coated nickel-cobalt lithium manganate material, and it mainly solves
Certainly the specific discharge capacity of the nickle cobalt lithium manganate existing for prior art is relatively low, and nickelic nickle cobalt lithium manganate, nickel and lithium are at material
Internal easily generation mixing phenomenon causes the precipitation of lithium, when air humidity is bigger, the technical problem that analysis lithium phenomenon the most seriously waits.
The above-mentioned technical problem of the present invention is mainly addressed by following technical proposals:
The preparation method of a kind of height ratio capacity graphene coated nickel-cobalt lithium manganate material of the present invention, it is characterised in that described
Method include:
A. nickle cobalt lithium manganate powder is prepared, as by the raw material of graphene coated；
B. through optimized choice one containing K2SO4Aqueous solution as electrolyte solution, add in reaction vessel, reaction is held
Device can be glass or ceramic utensil and plastic containers；
C. it is pressed into the bar raw material as making Graphene with native graphite or powdered graphite, also serves as a positive pole work electricity
Pressure, connects bar shaped native graphite by tungsten filament silver soldering；Do negative pole with a platinum filament to be positioned in reaction vessel；
D. add 2～4V voltage is on graphite electrode, and SO4 2-It is slowly inserted in graphite crystal boundary；
E. applying high offset voltage+8～16V, before applying+10V offset voltage, native graphite remains as a monolithic,
The highest offset voltage adds, graphite flake start expand, graphite start oxidation, and then add a negative offset voltage-8～
16V is on graphite electrode, and oxidized graphite reduces, and so repeats, graphite fast dissociation, until resolving into bilayer graphene
Thin slice, thickness is 2～4nm, is diffused in solution, floats on bath surface；
F. K will be floated on2SO4Graphene on solution is collected, and is filtered by filter membrane vacuum, is removed by big graphite granule
After falling, use water cyclic washing, remove residual acid solution；
G. dried, finally the powder of the graphene film obtained is dispersed in dimethyl formamide solution, by temperature
The water-bath of sum carries out supersound process；
H. being centrifuged suspension separating, after centrifugation aaerosol solution, get product graphene platelet；
I. it is evenly coated on nickel-cobalt lithium manganate material surface, at 170～200 DEG C to realize 3～4 layer graphene thin slices
Under the conditions of graphene platelet is distributed to DMF(dimethylformamide) in solution, under conditions of stirring, by the graphite of gained
Alkene solution drop by drop adds in nickel-cobalt lithium manganate material powder, above-mentioned material is placed in after dripping vacuum drying oven and dries
Dry, obtain graphene coated nickel-cobalt lithium manganate material, in this material, the content of Graphene is 0.2～3wt%.
Above-mentioned step e is the committed step obtaining excellent conductive rate graphene platelet, adjusts dutycycle and (i.e. reduces positive voltage
Ratio with negative voltage) make oxidization time reduce recovery time growth, greatly reduce the defect that Graphene oxidation produces；Step
I has conclusive effect, is added dropwise over by Graphene DMF solution on the nickel-cobalt lithium manganate material in stirring, is by model moral
Graphene platelet is evenly coated on nickel-cobalt lithium manganate material by Hua Li.
Graphene coated nickel-cobalt lithium manganate material prepared by the present invention, is the stone utilizing DMF dispersion electrochemical process to prepare
Ink alkene sheet, and Graphene DMF solution is added dropwise in the nickel-cobalt lithium manganate material in stirring, meanwhile DMF gradually volatilizees,
Its clad is uniform, and thickness only has 2-10nm, is effectively improved the conductivity of material, enhances ion at electrode surface
Transmission speed so that the specific capacity of graphene coated nickel-cobalt lithium manganate material is higher than nickelic nickel-cobalt lithium manganate material.According to this
The understanding that people is current, two kinds of synergism promote to there occurs reversible redox reaction between lithium ion and Graphene, thus
Improve the specific capacity of material.The nickle cobalt lithium manganate powder of the present invention, uses CN102709541A " a kind of high-density lithium ion electricity
The preparation method of pond anode material nickel cobalt manganic acid lithium and special calcination furnace " method prepare.
As preferably, described K2SO4The H that aqueous solution is mass concentration 98%2SO4Put into deionized water, and add
The KOH solution configuration of mass concentration 30% forms as electrolyte, its pH value 10～12.
As preferably, between size 5-20mm of described natural graphite flakes or highly directional type cracking graphite (HOPG) size
For 1.5cm × 1.5cm × 0.3mm.
As preferably, described positive pole, negative pole must be parallel at a distance of 50mm.
As preferably, described step d adds 2～the 1 minute time on graphite electrode of 4V voltage；Step e applies height
Offset voltage+8～the 16V time on graphite electrode is 1～4 second, adds a negative offset voltage-8～16V in graphite electrode
On time be 2～10 seconds, apply height offset voltage repeat about 10 minutes working times.
As preferably, described step g carries out supersound process 5 minutes by gentle water-bath.
As preferably, described step h centrifuge RPMs 2500 revs/min.
As preferably, in described step a, the chemical formula of material is Li(Ni0.5Co0.2Mn0.3) O2, or Li
(Ni0.4Co0.2Mn0.4) O2, or Li(Ni1/3Co1/3Mn1/3) O2。
As preferably, the graphene platelet thickness obtained by described step h is 2 4nm.
As preferably, the concentration of described Graphene dimethyl formamide solution is 100 1000ppm, graphene coated
Its graphene coated layer thickness of nickel-cobalt lithium manganate material is 2-10nm.
Therefore, the present invention utilize Graphene pass through Van der Waals force be uniformly coated with nickel-cobalt lithium manganate material surface method prepare
Graphene coated nickel-cobalt lithium manganate material, improves the conductivity of electrode material, enhances the ion transmission speed at electrode surface
Degree so that the specific capacity of graphene coated nickel-cobalt lithium manganate material is higher than nickelic nickel-cobalt lithium manganate material.Current according to me
Understanding, two kinds of synergism promote to there occurs reversible redox reaction between lithium ion and Graphene, thus improve
The specific capacity of material.
Accompanying drawing explanation
Accompanying drawing 1 is the 0.2C discharge curve that the present invention is dressed up button cell test by embodiment 1；
Accompanying drawing 2 is the 0.2C discharge curve that the present invention is dressed up button cell test by embodiment 2；
Accompanying drawing 3 is the 0.2C discharge curve that the present invention is dressed up button cell test by embodiment 3.
Detailed description of the invention
Below by embodiment, and combine accompanying drawing, technical scheme is described in further detail.
Embodiment 1: the preparation method of a kind of height ratio capacity graphene coated nickel-cobalt lithium manganate material of this example, its step
For:
A, the employing patent of invention CN102709541A " system of a kind of high-density lithium ion battery anode material nickel cobalt manganic acid lithium
Preparation Method and special calcination furnace " method prepare nickle cobalt lithium manganate powder, the chemical formula of material is Li(Ni0.5Co0.2Mn0.3) O2,
As by the raw material of graphene coated.
B, as positive pole and prepare Graphene using natural flake graphite (NGF) (between average-size about 5～20 millimeters)
Raw material, strip graphite end face first with Φ 1mm hole, after cleaning out, tungsten filament is inserted in the hole and with silver soldering, tungsten filament is welded, with
Stripe shape graphite is integrated, and is inserted into the solion as anode, only graphite impregnation in solution, and platinum filament is as ground electrode
(negative pole), is placed in parallel with graphite flake, and with strip graphite-phase away from 50mm, takes the H of (2.4-4.8 gram)2SO4(98%) put into
100mL deionized water and addition 11mL30%KOH solution are as electrolyte, and pH value 10～12 adds in reaction vessel, reaction vessel
It it is the glass beaker of a 250mL.First adding+2.5V low bias voltage on graphite electrode, the time is 1 minute, then add one high
The offset voltage+10V(time be 2 seconds) and high bias voltage-10V voltage (time is 5 seconds), so repeat alternately
Voltage, the time is about 10 minutes, i.e. obtains the Graphene of suspended state.Dividing the Graphene 100nm of suspension with Shanghai Chu Ding
After the porous filter vacuum of the DL-01 type that analysis Instrument Ltd. produces is collected by filtration, laggard with deionized water cyclic washing
Row is dried, and drying equipment is the DZF-6051 type vacuum drying oven that Shanghai Zhongyou's instrument and equipment company limited produces, the stone obtained
Ink alkene thin film powder sheet is dispersed in dimethylformamide (DMF) solution, is processed 5 minutes by gentle water bath sonicator, with
Producing the useless graphite granule stripped down to removing, be centrifuged suspension separating, using that Hunan Province is triumphant reaches industry
The TD6M type desk centrifuge that Development Co., Ltd produces, revolution is 2500 revs/min, the most available after centrifugation aaerosol solution
High-quality, large-area graphene platelet.The experiment of all these electrochemical strippings is carried out at room temperature 25 DEG C ± 3 DEG C.
C, nickel-cobalt lithium manganate material 99.2g obtained in a is put into agitator tank stirring, by made in b under the conditions of 180 DEG C
The graphene film 0.8g obtained is distributed in 1599.8gDMF solution, and is added dropwise in above-mentioned stirring by Graphene DMF solution
In nickel-cobalt lithium manganate material, after dripping, above-mentioned material is placed in the drying of 110-140 DEG C of vacuum drying oven, obtains graphene coated
Nickel-cobalt lithium manganate material, in this material, the content of Graphene is 0.8wt%.
Gained graphene coated Li(Ni0.5Co0.2Mn0.3) O2Material (Graphene content 0.8wt%) is assembled into CR2016 button
Formula battery, 0.2C specific discharge capacity reaches 196mAh/g(2.5～4.3V, vs.Li).Discharge curve such as Fig. 1.
Embodiment 2: the preparation method of a kind of height ratio capacity graphene coated nickel-cobalt lithium manganate material of this example, its step
For:
A, the employing patent of invention CN102709541A " system of a kind of high-density lithium ion battery anode material nickel cobalt manganic acid lithium
Preparation Method and special calcination furnace " method prepare nickle cobalt lithium manganate powder, the chemical formula of material is Li(Ni0.5Co0.2Mn0.3) O2,
As by the raw material of graphene coated.
B, as positive pole and prepare Graphene using natural flake graphite (NGF) (between average-size about 5～20 millimeters)
Raw material, strip graphite end face first with Φ 1mm hole, after cleaning out, tungsten filament is inserted in the hole and with silver soldering, tungsten filament is welded, with
Stripe shape graphite is integrated, and is inserted into the solion as anode, only graphite impregnation in solution, and platinum filament is as ground electrode
(negative pole), is placed in parallel with graphite flake, and with strip graphite-phase away from 50mm, takes the H of (2.4-4.8 gram)2SO4(98%) put into
100mL deionized water and addition 11mL30%KOH solution are as electrolyte, and pH value 10～12 adds in reaction vessel, reaction vessel
It it is the glass beaker of a 250mL.First adding+2.5V low bias voltage on graphite electrode, the time is 1 minute, then add one high
The offset voltage+10V(time be 2 seconds) and high bias voltage-10V voltage (time is 5 seconds), so repeat alternately
Voltage, the time is about 10 minutes, i.e. obtains the Graphene of suspended state.Dividing the Graphene 100nm of suspension with Shanghai Chu Ding
After the porous filter vacuum of the DL-01 type that analysis Instrument Ltd. produces is collected by filtration, laggard with deionized water cyclic washing
Row is dried, and drying equipment is the DZF-6051 type vacuum drying oven that Shanghai Zhongyou's instrument and equipment company limited produces, the stone obtained
Ink alkene thin film powder sheet is dispersed in dimethylformamide (DMF) solution, is processed 5 minutes by gentle water bath sonicator, with
Producing the useless graphite granule stripped down to removing, be centrifuged suspension separating, using that Hunan Province is triumphant reaches industry
The TD6M type desk centrifuge that Development Co., Ltd produces, revolution is 2500 revs/min, the most available after centrifugation aaerosol solution
High-quality, large-area graphene platelet.The experiment of all these electrochemical strippings is carried out at room temperature 25 DEG C ± 3 DEG C.
C, nickel-cobalt lithium manganate material 98.5g obtained in a is put in agitator tank and stirs, by institute in b under the conditions of 180 DEG C
The graphene film 1.5g prepared is distributed in 2998.5gDMF solution, and is added dropwise in above-mentioned stirring by Graphene DMF solution
Nickel-cobalt lithium manganate material in, after dripping, above-mentioned material is placed in the drying of 110-140 DEG C of vacuum drying oven, obtains Graphene bag
Covering nickel-cobalt lithium manganate material, in this material, the content of Graphene is 1.5wt%.
Gained graphene coated Li(Ni0.5Co0.2Mn0.3) O2Material (Graphene content 1.5wt%) is assembled into CR2016 button
Formula battery, 0.2C specific discharge capacity reaches 207mAh/g(2.5～4.3V, vs.Li).Discharge curve such as Fig. 2.
Embodiment 3: the preparation method of a kind of height ratio capacity graphene coated nickel-cobalt lithium manganate material of this example, its step
For:
A, the employing patent of invention CN102709541A " system of a kind of high-density lithium ion battery anode material nickel cobalt manganic acid lithium
Preparation Method and special calcination furnace " method prepare nickle cobalt lithium manganate powder, the chemical formula of material is Li(Ni0.5Co0.2Mn0.3) O2,
As by the raw material of graphene coated.
B, as positive pole and prepare Graphene using natural flake graphite (NGF) (between average-size about 5～20 millimeters)
Raw material, strip graphite end face first with Φ 1mm hole, after cleaning out, tungsten filament is inserted in the hole and with silver soldering, tungsten filament is welded, with
Stripe shape graphite is integrated, and is inserted into the solion as anode, only graphite impregnation in solution, and platinum filament is as ground electrode
(negative pole), is placed in parallel with graphite flake, and with strip graphite-phase away from 50mm, takes the H of (2.4-4.8 gram)2SO4(98%) put into
100mL deionized water and addition 11mL30%KOH solution are as electrolyte, and pH value 10～12 adds in reaction vessel, reaction vessel
It it is the glass beaker of a 250mL.First adding+2.5V low bias voltage on graphite electrode, the time is 1 minute, then add one high
The offset voltage+10V(time be 2 seconds) and high bias voltage-10V voltage (time is 5 seconds), so repeat alternately
Voltage, the time is about 10 minutes, i.e. obtains the Graphene of suspended state.Dividing the Graphene 100nm of suspension with Shanghai Chu Ding
After the porous filter vacuum of the DL-01 type that analysis Instrument Ltd. produces is collected by filtration, laggard with deionized water cyclic washing
Row is dried, and drying equipment is the DZF-6051 type vacuum drying oven that Shanghai Zhongyou's instrument and equipment company limited produces, the stone obtained
Ink alkene thin film powder sheet is dispersed in dimethylformamide (DMF) solution, is processed 5 minutes by gentle water bath sonicator, with
Producing the useless graphite granule stripped down to removing, be centrifuged suspension separating, using that Hunan Province is triumphant reaches industry
The TD6M type desk centrifuge that Development Co., Ltd produces, revolution is 2500 revs/min, the most available after centrifugation aaerosol solution
High-quality, large-area graphene platelet.The experiment of all these electrochemical strippings is carried out at room temperature 25 DEG C ± 3 DEG C.
C, nickel-cobalt lithium manganate material 98g obtained in a is put in agitator tank and stirs, by made in b under the conditions of 180 DEG C
The graphene film 2g obtained is distributed in 3998gDMF solution, and Graphene DMF solution is added dropwise over the nickel cobalt in above-mentioned stirring
In lithium manganate material, after dripping, above-mentioned material is placed in the drying of 110-140 DEG C of vacuum drying oven, obtains graphene coated nickel cobalt
Lithium manganate material, in this material, the content of Graphene is 2wt%.
Gained graphene coated Li(Ni0.5Co0.2Mn0.3) O2Material (Graphene content 2wt%) is assembled into CR2016 button
Battery, 0.2C specific discharge capacity reaches 212mAh/g(2.5～4.3V, vs.Li).Discharge curve such as Fig. 3.
Graphene coated Li(Ni obtained by above-mentioned three kinds of embodiments0.5Co0.2Mn0.3) O2Material, its 0.2C specific discharge capacity
It is above nickelic nickel-cobalt lithium manganate material (195mAh/g).
In sum, the present invention solves the problem that the nickel-cobalt lithium manganate material specific capacity existing for prior art is low, carries
Before complete in electric automobile development in science and technology " 12 " ad hoc planning lithium-ion-power cell energy density in 2015 reached
The target of 160wh/kg, the target reaching 250wh/kg for the year two thousand twenty lithium-ion-power cell energy density has established solid base
Plinth.
The foregoing is only the specific embodiment of the present invention, but the architectural feature of the present invention is not limited thereto, Ren Heben
The technical staff in field is in the field of the invention, and change or the modification made all are contained among the scope of the claims of the present invention.
Claims (6)
1. the preparation method of a height ratio capacity graphene coated nickel-cobalt lithium manganate material, it is characterised in that described method bag
Include:
A. nickle cobalt lithium manganate powder is prepared, as by the raw material of graphene coated；
B. with containing K2SO4Aqueous solution as electrolyte solution, add in reaction vessel, K2SO4Aqueous solution be mass concentration 98%
H2SO4Put into deionized water, and the KOH solution adding mass concentration 30% configures, its pH value 10～12, reaction vessel
It is glass or ceramic utensil and plastic containers；
C. it is pressed into the bar raw material as making Graphene with native graphite, also serves as a work positive pole, by tungsten filament with silver soldering even
Connect bar shaped native graphite；Doing negative pole with a platinum filament to be positioned in reaction vessel, positive pole, negative pole must be parallel at a distance of 50mm；
D. add 2～4V voltage is on graphite electrode, 1 minute time, make SO4 2-It is slowly inserted in graphite crystal boundary；
E. applying high offset voltage+8～16V, the time is 1～4 second, and before applying high offset voltage, native graphite remains as one
Individual monolithic, the highest offset voltage adds, graphite flake starts to expand, and graphite starts oxidation, and then adds a negative skew
Voltage-8～16V are on graphite electrode, and the time is 2～10 seconds, and oxidized graphite reduces, and so repeats, the work of repetition
Time is 10 minutes, graphite fast dissociation, until resolving into bilayer graphene thin slice, thickness is 2～4 nm, is diffused into solution
In, float on bath surface；
F. K will be floated on2SO4Graphene on solution is collected, and is filtered by filter membrane vacuum, after being removed by big graphite granule, uses
Water cyclic washing, removes residual acid solution；
G. dried, finally the powder of the graphene film obtained is dispersed in dimethyl formamide solution, by gentleness
Water-bath carries out supersound process；
H. being centrifuged suspension separating, after centrifugation aaerosol solution, get product graphene platelet；
I. nickel-cobalt lithium manganate material is put into high-temperature stirring in agitator tank, under the conditions of 170～200 DEG C, graphene platelet is disperseed
In dimethyl formamide solution, the concentration of Graphene dimethyl formamide solution is 100 1000ppm, and by Graphene two
Methylformamide solution is added dropwise in the nickel-cobalt lithium manganate material in above-mentioned stirring, after dripping, above-mentioned material is placed in vacuum
Drying baker is dried, and obtains graphene coated nickel-cobalt lithium manganate material, and in this material, the content of Graphene is 0.2 3wt%, graphite
Alkene cladding its graphene coated layer thickness of nickel-cobalt lithium manganate material is 2-10nm.
The preparation method of a kind of height ratio capacity graphene coated nickel-cobalt lithium manganate material the most according to claim 1, it is special
Levy and be that described native graphite is natural graphite flakes, between size 5-20mm of natural graphite flakes.
The preparation method of a kind of height ratio capacity graphene coated nickel-cobalt lithium manganate material the most according to claim 1, it is special
Levy and be that described step g carries out supersound process 5 minutes by gentle water-bath.
The preparation method of a kind of height ratio capacity graphene coated nickel-cobalt lithium manganate material the most according to claim 1, it is special
Levy and be described step h centrifuge RPMs 2500 revs/min.
The preparation method of a kind of height ratio capacity graphene coated nickel-cobalt lithium manganate material the most according to claim 1, it is special
Levy and be in described step a that the chemical formula of material is Li(Ni0.5Co0.2Mn0.3) O2, or Li(Ni0.4Co0.2Mn0.4) O2, or Li
(Ni1/3Co1/3Mn1/3) O2。
The preparation method of a kind of height ratio capacity graphene coated nickel-cobalt lithium manganate material the most according to claim 1, it is special
Levy and be that the graphene platelet thickness obtained by described step h is 2 4nm.
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| CN104828878B (en) * | 2015-03-31 | 2017-06-09 | 盐城师范学院 | A kind of preparation method of the nickel ion doped material of graphene coated |
| JP6753050B2 (en) * | 2015-10-26 | 2020-09-09 | 住友金属鉱山株式会社 | A positive electrode active material for a non-aqueous electrolyte secondary battery, and a non-aqueous electrolyte secondary battery using the positive electrode active material. |
| CN106328904B (en) * | 2016-10-26 | 2019-01-29 | 北京光科博冶科技有限责任公司 | Height ratio capacity nitrogen-doped graphene nickle cobalt lithium manganate composite material and preparation method |
| CN109461927A (en) * | 2017-12-21 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of compound nickel-cobalt-manganese multi positive electrode of high magnification and preparation method thereof |
| CN110416491A (en) * | 2019-08-26 | 2019-11-05 | 贵州大学 | Modified ternary nickel cobalt manganese electrode of a kind of graphene coated and preparation method thereof |
| CN110518208A (en) * | 2019-08-26 | 2019-11-29 | 贵州大学 | A kind of preparation method of graphene coated cobalt acid lithium electrode |
| CN111969204B (en) * | 2020-07-29 | 2021-10-19 | 宁夏汉尧石墨烯储能材料科技有限公司 | Lithium ion battery electrode containing nano-grade graphene coated single crystal cathode material |
| CN114275826B (en) * | 2021-12-14 | 2023-02-28 | 湖北容百锂电材料有限公司 | Graphene carbon surface modified nickel cobalt lithium manganate ternary positive electrode material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102891311A (en) * | 2012-10-23 | 2013-01-23 | 中国科学院过程工程研究所 | Graphene-Li(NixCoyMnz)O2 compound electrode material of lithium ion battery and preparation method of graphene-Li(NixCoyMnz)O2 compound electrode material |
| CN103204494A (en) * | 2012-01-16 | 2013-07-17 | 中央研究院 | Device and method used for scale production of graphene and graphene oxide |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102891311A (en) * | 2012-10-23 | 2013-01-23 | 中国科学院过程工程研究所 | Graphene-Li(NixCoyMnz)O2 compound electrode material of lithium ion battery and preparation method of graphene-Li(NixCoyMnz)O2 compound electrode material |
Non-Patent Citations (1)
| Title |
|---|
| "High-Quality Thin Graphene Films from Fast Electrochemical Exfoliation";Ching-Yuan Su等;《ACS Nano》;20110210;第5卷(第3期);第2333页左栏第2段-第2335页左栏第1段，第2337页左栏第1段，附图1（a）-1（c） * |
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