CN104538612B - A kind of preparation method of nickel aluminium lithium anode material - Google Patents
A kind of preparation method of nickel aluminium lithium anode material Download PDFInfo
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- CN104538612B CN104538612B CN201410793082.XA CN201410793082A CN104538612B CN 104538612 B CN104538612 B CN 104538612B CN 201410793082 A CN201410793082 A CN 201410793082A CN 104538612 B CN104538612 B CN 104538612B
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- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001148 Al-Li alloy Inorganic materials 0.000 title claims abstract description 8
- 239000010405 anode material Substances 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011149 active material Substances 0.000 claims abstract description 23
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 239000011651 chromium Substances 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 238000005245 sintering Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 18
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 claims description 4
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910010092 LiAlO2 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- KYUOTPSBWVNTFR-UHFFFAOYSA-M O[Ni]O[Co] Chemical compound O[Ni]O[Co] KYUOTPSBWVNTFR-UHFFFAOYSA-M 0.000 description 1
- NXPZICSHDHGMGT-UHFFFAOYSA-N [Co].[Mn].[Li] Chemical compound [Co].[Mn].[Li] NXPZICSHDHGMGT-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical class [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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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
- H01M4/525—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of preparation method of nickel aluminium lithium anode material, the chemical formula of the active material of the positive electrode is Li1.02Ni1‑x‑yAlxZryO2, wherein：X=0.22 0.3, y=0.12 0.16, the method comprises the steps：（1）Wet method prepares active material presoma,（2）Solid sintering technology prepares active material Li1.02Ni1‑x‑yAlxZryO2,（3）Surface chromium is modified.Positive electrode prepared by the present invention, adopt wet method to prepare and solid sintering technology is combined to obtain the active material of higher energy density, and adulterated using Zr and Cr surface modification treatment improve material high temperature circulation stability so that the material possesses higher specific capacity and high-temperature electrochemistry stability.Therefore the composite for lithium ion battery when, especially at high temperature application scenario, with higher capacity and long service life.
Description
Technical field
The present invention relates to a kind of preparation method of nickel aluminium lithium anode material.
Background technology
Used as a kind of green secondary cell, with lightweight, small volume, discharge platform is high, capacity is big, follow for lithium ion battery
The advantages of ring life-span length, memory-less effect, the mobile electronic electrical equipment such as mobile phone, camera, notebook computer is widely used to, with
When be also increasingly used for the fields such as artificial satellite, Aero-Space, electric automobile.
The lithium ion battery being used widely at present, its positive electrode are just being experiencing constantly in updating and improveing.Lithium
Ion battery positive electrode has a lot of systems, currently used for the lithium and cobalt oxides series for mainly having stratiform of practical application
(LiCoO2), the lithium nickel oxide series (LiNiO of stratiform2) and spinelle shape lithium manganese oxide series (LiMn2O4).But,
Above-mentioned system all has significant deficiency, have impact on their practical application.The polynary electrode material of nickel aluminium lithium is to send out in recent years
The new type lithium ion battery positive electrode that exhibition is got up, it has concentrated LiAlO2And LiNiO2The advantage of material.Because with relatively inexpensive
Nickel and manganese instead of the cobalt of (or more) 2/3rds in cobalt acid lithium, therefore have a clear superiority in terms of its cost.But mesh
The hot environment stable circulation performance of front pure manganese cobalt lithium material is not fine.
Content of the invention
A kind of preparation method of nickel aluminium lithium anode material of present invention offer, the positive electrode prepared using the method, have
Higher specific capacity and high temperature circulation stability.
To achieve these goals, the preparation method of a kind of nickel aluminium lithium anode material that the present invention is provided, the positive electrode
Active material chemical formula be Li1.02Ni1-x-yAlxZryO2, wherein：X=0.22-0.3, y=0.12-0.16, the method include
Following steps：
（1）Wet method prepares active material presoma
By nickel, the soluble-salt Ni in molar ratio of aluminium2+∶Al3+=1-x-y: x is hybridly prepared into the 1.5-2mol/L aqueous solution
One；Hydrogen peroxide is configured to the 3-4mol/L aqueous solution two, NaOH is configured to the 4-5mol/L aqueous solution and adds 1-2mol/
The ammoniacal liquor of L, the volume ratio of the two are (4-8): 1, the aqueous solution three is obtained, prepare three kinds of aqueous solution are added with agitating device
Reactor in, the charging rate of solution one and two is 15-20ml/min, adjusts the charging rate of solution three to control reaction
The pH value of system is stirred with the speed of 500-600rpm, is heated to 60-75 DEG C between 12-14, is terminated after reaction 10-15h,
Nickel aluminium hydroxide is then filtered off, after nickel aluminium hydroxide is washed with deionized filter 23-5 times, in 120-130 DEG C of vacuum
Dry in drying box and obtain nickel aluminium hydroxide presoma；
（2）Solid sintering technology prepares active material Li1.02Ni1-x-yAlxZryO2
By above-mentioned nickel aluminium hydroxide presoma, lithium hydroxide, zirconium hydroxide according to mol ratio 1.02:1-y：Y ball milling is mixed
Close fully, in air atmosphere, at 950-1000 DEG C, 10-15h is incubated, be naturally cooling to room temperature, crushing and classification, prepared activity
Material Li1.02Ni1-x-yAlxZryO2；
（3）Surface chromium is modified
Compound concentration is the chromium nitrate solution of 0.1-0.2mol/L, by above-mentioned active material Li1.02Ni1-x-yAlxZryO2Place
Particle diameter is managed into for adding in the chromium nitrate solution after 10-15 μm of particle, mixture is formed, phosphoric acid solution adds the mixture to enter
Row reaction, makes the positive active material particle surface form phosphoric acid layers of chrome, and wherein the chromium phosphate clad is in the positive pole composite wood
Mass percent in material particle is 0.5-1%, is heat-treated the active material that the surface has phosphoric acid layers of chrome at 400-550 DEG C
Particle 6-10h, obtains positive electrode.
Positive electrode prepared by the present invention, adopts wet method to prepare and solid sintering technology is combined to obtain higher energy density
Active material, and adulterated using Zr and Cr surface modification treatment improve material high temperature circulation stability so that the material
Possesses higher specific capacity and high-temperature electrochemistry stability.Therefore the composite especially exists when for lithium ion battery
During high temperature application scenario, with higher capacity and long service life.
Specific embodiment
Embodiment one
The chemical formula of the active material of the positive electrode of the present embodiment is Li1.02Ni0.66Al0.22Zr0.12O2.
By nickel, the soluble-salt Ni in molar ratio of aluminium2+∶Al3+Be hybridly prepared into the 1.5mol/L aqueous solution at=0.66: 0.22
One；Hydrogen peroxide is configured to the 3mol/L aqueous solution two, NaOH is configured to the 4mol/L aqueous solution and adds the ammonia of 1mol/L
Water, the volume ratio of the two are 4: 1, obtain the aqueous solution three, and prepare three kinds of aqueous solution are added the reactor with agitating device
In, the charging rate of solution one and two is 15ml/min, adjusts the charging rate of solution three to control the pH value of reaction system
Between 12, stirred with the speed of 500rpm, 60 DEG C be heated to, terminate after reaction 15h, nickel aluminium hydroxide is then filtered off,
After nickel aluminium hydroxide is washed with deionized filter 23 time, dry in 120 DEG C of vacuum drying chambers before obtaining nickel aluminium hydroxide
Drive body.
By above-mentioned nickel aluminium hydroxide presoma, lithium hydroxide, zirconium hydroxide according to mol ratio 1.02:0.88：0.12 ball
Mill mixing fully, in air atmosphere, is incubated 15h at 950 DEG C, is naturally cooling to room temperature, crushing and classification, prepared active material
Li1.02Ni0.66Al0.22Zr0.12O2.
Compound concentration is the chromium nitrate solution of 0.1-0.2mol/L, by above-mentioned active material Li1.02Ni0.66Al0.22Zr0.12O2
Particle diameter is processed into for adding in the chromium nitrate solution after 10-15 μm of particle, mixture is formed, phosphoric acid solution adds the mixture
Reacted, make the positive active material particle surface that phosphoric acid layers of chrome is formed, the wherein chromium phosphate clad is compound in the positive pole
Mass percent in material granule is 0.5%, is heat-treated the active material particle that the surface has phosphoric acid layers of chrome at 400 DEG C
10h, obtains positive electrode.
Embodiment two
The chemical formula of the active material of the positive electrode of the present embodiment is Li1.02N0.54Al0.3Zr0.16O2.
By nickel, the soluble-salt Ni in molar ratio of aluminium2+∶Al3+Be hybridly prepared into the 2mol/L aqueous solution one at=0.54: 0.3；
Hydrogen peroxide is configured to the 4mol/L aqueous solution two, NaOH is configured to the 5mol/L aqueous solution and the ammoniacal liquor of 2mol/L is added,
The volume ratio of the two is 8: 1, obtains the aqueous solution three, and prepare three kinds of aqueous solution are added in the reactor with agitating device,
The charging rate of solution one and two is 20ml/min, adjusts the charging rate of solution three to control the pH value of reaction system to exist
14, stirred with the speed of 600rpm, 75 DEG C are heated to, terminate after reaction 10h, be then filtered off nickel aluminium hydroxide, nickel aluminium hydrogen
Oxide is washed with deionized after filtering 5 times, dries and obtain nickel aluminium hydroxide presoma in 130 DEG C of vacuum drying chambers.
By above-mentioned nickel aluminium hydroxide presoma, lithium hydroxide, zirconium hydroxide according to mol ratio 1.02:0.84：0.16 ball
Mill mixing fully, in air atmosphere, is incubated 10-15h at 950-1000 DEG C, is naturally cooling to room temperature, and crushing and classification is obtained
Active material Li1.02N0.54Al0.3Zr0.16O2.
Compound concentration is the chromium nitrate solution of 0.2mol/L, by above-mentioned active material Li1.02N0.54Al0.3Zr0.16O2Process
Become particle diameter for adding in the chromium nitrate solution after 10-15 μm of particle, mixture is formed, phosphoric acid solution adds the mixture to carry out
Reaction, makes the positive active material particle surface form phosphoric acid layers of chrome, and wherein the chromium phosphate clad is in the anode composite material
Mass percent in particle is 1%, is heat-treated the active material particle 6h that the surface has phosphoric acid layers of chrome, obtains at 550 DEG C
Positive electrode.
Comparative example
By nickel sulfate, cobaltous sulfate and aluminum sulfate Ni in molar ratio2+∶Co2+∶Al3+Be hybridly prepared into at=0.7: 0.25: 0.05
The aqueous solution of 1mol/L, potassium peroxydisulfate is configured to the aqueous solution of 2mol/L, and potassium hydroxide is configured to the solution 2L of 3mol/L
And add the ammoniacal liquor of 0.5L 0.75mol/L.Then by the mixing salt solution for preparing with potassium persulfate solution all with 10ml/min
Flow velocity cocurrent add in 12L reactor with agitating device, be stirred and heated to 35 DEG C with the speed of 450rpm, adjust alkali
The charging rate of solution terminates after reaction 8h, is then filtered off spherical hydroxyl to control the pH value of reaction system between 11-11.5
Base cobalt nickel oxide aluminium presoma.Again spherical hydroxy nickel oxide cobalt aluminium is washed with deionized and filters after 6 times, in 120 DEG C of vacuum
12h is dried in drying box obtains presoma.The presoma scanning electron microscope (SEM) photograph is as shown in figure 1, pattern is spherical and spherical；Before this
Body X-ray diffractogram is driven as shown in Fig. 2 consistent with standard card 06-0141.Again by lithium hydroxide and presoma with 1.06: 1 ratio
After example is mixed, be placed in flowing pure oxygen atmosphere stove in 700 DEG C of roasting 10h, classification crushed after cooling, obtain aluminum-doped nickel cobalt
Sour lithium material.
By above-described embodiment one, two and comparative example products therefrom respectively with conductive carbon black, binding agent PVDF (polyvinylidene fluoride
Alkene) in mass ratio 90: 5: 5 mixing, it is coated on Copper Foil, is that electrolyte is the LiPF of 1mol/L to pole with metal lithium sheet6Molten
Liquid, solvent are the mixed solvent of EC, DEC and EMC, and volume ratio is 1: 1: 1.Argon gas protection glove box in by positive pole, negative pole,
Electrolyte, barrier film and battery case are assembled into button cell.Electrical property survey is carried out under the hot environment that test temperature is 50 DEG C
Examination, after tested the embodiment one with two material compared with the product of comparative example, specific capacity improves 15-18% first, using the longevity
Life brings up to more than one times.
Claims (1)
1. a kind of preparation method of nickel aluminium lithium anode material, the chemical formula of the active material of the positive electrode is Li1.02Ni1-x- yAlxZryO2, wherein：X=0.22-0.3, y=0.12-0.16, the method include following step：
（1）Wet method prepares active material presoma
By nickel, the soluble-salt Ni in molar ratio of aluminium2+∶Al3+=1-x-y: x is hybridly prepared into the 1.5-2mol/L aqueous solution one；Will
Hydrogen peroxide is configured to the 3-4mol/L aqueous solution two, NaOH is configured to the 4-5mol/L aqueous solution and adds the ammonia of 1-2mol/L
Water, the volume ratio of the two are (4-8): 1, the aqueous solution three is obtained, prepare three kinds of aqueous solution are added with the anti-of agitating device
Answer in kettle, the charging rate of solution one and two is 15-20ml/min, the charging rate of solution three is adjusted to control reaction system
PH value between 12-14, stirred with the speed of 500-600rpm, be heated to 60-75 DEG C, terminate after reaction 10-15h, then
Nickel aluminium hydroxide is filtered out, after nickel aluminium hydroxide is washed with deionized filter 23-5 times, is vacuum dried in 120-130 DEG C
Dry in case and obtain nickel aluminium hydroxide presoma；
（2）Solid sintering technology prepares active material Li1.02Ni1-x-yAlxZryO2
By above-mentioned nickel aluminium hydroxide presoma, lithium hydroxide, zirconium hydroxide according to mol ratio 1.02:1-y：Y ball milling mixing is filled
Point, in air atmosphere, at 950-1000 DEG C, 10-15h is incubated, is naturally cooling to room temperature, crushing and classification, prepared active material
Li1.02Ni1-x-yAlxZryO2；
（3）Surface chromium is modified
Compound concentration is the chromium nitrate solution of 0.1-0.2mol/L, by above-mentioned active material Li1.02Ni1-x-yAlxZryO2It is processed into
Particle diameter forms mixture for adding in the chromium nitrate solution after 10-15 μm of particle, and phosphoric acid solution adds the mixture to carry out instead
Should, make the positive active material particle surface form phosphoric acid layers of chrome, wherein the chromium phosphate clad is in the anode composite material
Mass percent in grain is 0.5-1%, is heat-treated the active material particle that the surface has phosphoric acid layers of chrome at 400-550 DEG C
6-10h, obtains positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410793082.XA CN104538612B (en) | 2014-12-20 | 2014-12-20 | A kind of preparation method of nickel aluminium lithium anode material |
Applications Claiming Priority (1)
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| CN1599103A (en) * | 2004-08-04 | 2005-03-23 | 哈尔滨工业大学 | Method for preparing gradient covered LiNiO2 plus plate material for lithium ion battery |
| CN102347473A (en) * | 2010-08-02 | 2012-02-08 | 清华大学 | Anode composite material particle of lithium ion battery and preparation method thereof |
| CN102832389A (en) * | 2012-09-25 | 2012-12-19 | 湖南长远锂科有限公司 | High-nickel positive active material of surface-modified lithium ion battery and preparation method of positive active material |
| CN103975474A (en) * | 2011-12-19 | 2014-08-06 | 日立麦克赛尔株式会社 | Lithium secondary battery |
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| CN1599103A (en) * | 2004-08-04 | 2005-03-23 | 哈尔滨工业大学 | Method for preparing gradient covered LiNiO2 plus plate material for lithium ion battery |
| CN102347473A (en) * | 2010-08-02 | 2012-02-08 | 清华大学 | Anode composite material particle of lithium ion battery and preparation method thereof |
| CN103975474A (en) * | 2011-12-19 | 2014-08-06 | 日立麦克赛尔株式会社 | Lithium secondary battery |
| CN102832389A (en) * | 2012-09-25 | 2012-12-19 | 湖南长远锂科有限公司 | High-nickel positive active material of surface-modified lithium ion battery and preparation method of positive active material |
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