CN106410186A - Preparation method and application of lithium-rich layered oxide cathode material - Google Patents
Preparation method and application of lithium-rich layered oxide cathode material Download PDFInfo
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- CN106410186A CN106410186A CN201611009805.8A CN201611009805A CN106410186A CN 106410186 A CN106410186 A CN 106410186A CN 201611009805 A CN201611009805 A CN 201611009805A CN 106410186 A CN106410186 A CN 106410186A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 67
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000010406 cathode material Substances 0.000 title abstract 4
- 239000000463 material Substances 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 54
- 239000010405 anode material Substances 0.000 claims description 52
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- VUFYPLUHTVSSGR-UHFFFAOYSA-M hydroxy(oxo)nickel Chemical compound O[Ni]=O VUFYPLUHTVSSGR-UHFFFAOYSA-M 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910002983 Li2MnO3 Inorganic materials 0.000 abstract description 5
- 229910052804 chromium Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 229910003924 NixMn2 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910014411 LiNi1/2Mn1/2O2 Inorganic materials 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 229910005629 Li(Li0.20Ni0.13Co0.13Mn0.54)O2 Inorganic materials 0.000 description 1
- 229910005662 Li(Li0.2Ni0.2Mn0.6)O2 Inorganic materials 0.000 description 1
- 229910007499 Li1/3Mn2/3 Inorganic materials 0.000 description 1
- 229910002982 Li2MnO3 phase Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a lithium-rich layered oxide cathodee material. The chemical formula of the lithium-rich layered oxide cathode material is Li[Li<(1-2x)/3>Ni<x-y>M<2y>Mn<2/3-x/3-y>]O<2>, wherein x is greater than 0 and smaller than 0.5, y is greater than 0 and smaller than x, and M is one or a mixture of two or more than two of Fe, Co, Al and Cr in any proportion. The preparation method of the lithium-rich layered oxide cathode material comprises the following steps: firstly using a high-temperature solid-phase method to prepare an M-doped Li2MnO3 material, then mixing the M-doped Li2MnO3 material with an Li source material, an Ni source material and an Mn source material, and mixing at the temperature of 700 to 950 DEG C and roasting for 5 to 15 h so as to obtain the target object. The material prepared by the invention has the advantages of stable structure, easily controlled conditions, high batch stability and the like, and is suitable for scale production; and a button cell assembled by using the prepared lithium-rich layered oxide cathode material has the advantages of high first-time charging and discharging efficiency, small voltage attenuation, good cycle performance and the like.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, specifically a kind of lithium-rich oxide anode material
Preparation method and application.
Background technology
With the popularization of portable type electronic product, hybrid vehicle and pure electric automobile, lithium ion battery also obtains
More and more widely use.In recent years, for developing the lithium ion battery of high-energy-density, it is developed many high-energy-densities
Positive electrode.Wherein lithium-rich oxide anode material is excellent because having discharge capacity height, voltage platform width, environmental protection etc.
Put and cause further investigation.The expression formula of lithium-rich oxide material is Li (Li1/3-2x/3NixMn2/3-x/3)O2(0<x<1/
2), it can regard Li as2MnO3(stratified material is represented by Li [Li1/3Mn2/3]O2) material and LiNi1/2Mn1/2O2Material
The solid solution being formed, therefore, lithium-rich oxide material Li (Li1/3-2x/3NixMn2/3-x/3)O2Expression formula can also write a
[yLi2MnO3·(1-y)LiNi1/2Mn1/2O2], wherein a=2 (1+x)/3, y=(1-2x)/(1+x).
According to substantial amounts of document report, to Li (Li1/3-2x/3NixMn2/3-x/3)O2Material carries out metal ion mixing can be had
Effect improves its chemical property.For the modified lithium-rich oxidation of lithium-rich oxide anode material and metal M ion
The preparation method of thing positive electrode mainly has coprecipitation, sol-gal process and combustion method etc..Coprecipitation：Li et al. reports
A kind of Acetate Solution by Mn, Ni and Co and LiOH prepare hydroxide precursor through coprecipitation reaction, through washing
After dry and LiOH mixing and ball milling is uniform, prepare Li (Li through high-temperature roasting0.2Mn0.56Ni0.16Co0.08)O2The method of material
(Journal of Power Sources,2011,196,4821).Sol-gal process：Zheng et al. is first by Ni (NO3)2·
6H2O、Co(NO3)2·6H2O and Mn (NO3)2Wiring solution-forming, then by LiNO3It is slowly added to the mixed solution of appropriate citric acid
To in the mixed solution of above-mentioned transition metal, then with ammonia adjust above two solution mixed solution pH value be 7.0～
8.0, pass through two-step thermal processing and quenching after being evaporated, obtain designed Li (Li0.20Ni0.13Co0.13Mn0.54)O2Positive electrode
(Electrochimica Acta,2011,56,3071)；Ma et al. is prepared for Li also by similar method
[Li0.2Ni0.11Co0.11Mn0.54Al0.04]O2Material (Journal of Power Sources, 2015,277,393).2.Burning
Method：Hong et al., with the acetate of Li, Ni and Mn and nitrate as raw material, is configured to solution according to stoichiometric proportion, is filled
Divide and after being dried, gained xerogel is lighted, finally carry out high-temperature heat treatment and quenching again, that is, obtain required Li
(Li0.2Ni0.2Mn0.6)O2With Li (Li0.27Co0.20Mn0.53)O2Material (Solid State Ionics, 2005,176,1035).
Above-described preparation method, in order to reach the uniform mixing of metal ion, all employs metal ion Ni, Mn
It is simultaneously introduced the method being made into homogeneous solution or mix homogeneously with M, the lithium-rich oxide material prepared by these methods
There is higher specific discharge capacity, but its to there is also material structure unstable, in cyclic process, part layer structure is brilliant to point
Stone structure changes the problems such as voltage decline thus resulting in and capacity attenuation, and constraining its reality in lithium ion battery should
With.The present invention is by dopant M ion modification Li2MnO3Phase, then by modified Li2MnO3With Li source, Ni source and Mn source
Material mixing roasting is preparing a kind of preparation method of lithium-rich oxide.By retrieval, for doped lithium-rich
Oxide anode material Li [Li(1-2x)/3Nix-yM2yMn2/3-x/3-y]O2(0<x<0.5,0<y<X, M are in Fe, Co, Al and Cr
Plant or several), it is not yet found that similar report.
Content of the invention
The present invention seeks to the problems referred to above overcoming prior art to exist, provide a kind of lithium-rich oxide anode material
Preparation method and application.
Technical scheme：
A kind of preparation method of lithium-rich oxide anode material, the chemistry of described lithium-rich oxide anode material
Molecular formula is Li [Li(1-2x)/3Nix-yM2yMn2/3-x/3-y]O2, in formula：0<x<0.5,0<y<X, M are in Fe, Co, Al and Cr
Kind or the mixture of two or more arbitrary proportion；
Its preparation methods steps are as follows：
1) by Li source, Mn source and M source metal mix homogeneously, obtain mixture；
2) by said mixture under conditions of 400-750 DEG C roasting 5-80h, obtain the metal-doped Li of M2MnO3Material；
3) by Li metal-doped for above-mentioned M2MnO3Material is sufficiently mixed uniformly with Li source, Ni source and Mn source, obtains mixing material
Material；
4) by above-mentioned mixing material at 700-950 DEG C roasting 5-15h；
5) it is cooled to room temperature, obtain lithium-rich oxide anode material Li [Li(1-2x)/3Nix-yM2yMn2/3-x/3-y]O2.
Described step 1) in Li source be one of lithium carbonate, Lithium hydrate, lithium nitrate and Quilonorm (SKB) or two or more
The mixture of meaning ratio；Mn source is oxidation (sub-) manganese, hydroxide (sub-) manganese, hydroxyl oxidize manganese, manganese carbonate, manganese nitrate and manganese acetate
One of two or more arbitrary proportions mixture；M source metal is carbonate, hydroxide, nitrate and the acetic acid of M metal
One of salt or the mixture of two or more arbitrary proportion；The mol ratio in Li source, Mn source and M source metal is (2-4x):(1-
2x-3y):3y, in formula：0<x<0.5,0<y<x.
Described step 3) in Li source be one of lithium carbonate, Lithium hydrate, lithium nitrate and Quilonorm (SKB) or two or more
The mixture of meaning ratio；Ni source is oxidation (sub-) nickel, hydroxide (sub-) nickel, hydroxy nickel oxide, nickelous carbonate, nickel nitrate and nickel acetate
One of or two or more arbitrary proportion mixture；Mn source be oxidation (sub-) manganese, hydroxide (sub-) manganese, hydroxyl oxidize manganese,
The mixture of the two or more arbitrary proportion of one of manganese carbonate, manganese nitrate and manganese acetate；The metal-doped Li of M2MnO3Material with
The mol ratio of Li, Ni and Mn of being added is (1-2x)：3x:(3x-3y)/2:(3x+3y)/2, in formula：0<x<0.5,0<y<x.
A kind of application of lithium-rich oxide anode material, for preparing the positive pole material of height ratio capacity lithium ion battery
Material.
The invention has the beneficial effects as follows：
The lithium-rich oxide anode material of this method preparation is by modified M ion doping to Li2MnO3Xiang Zhong, effectively
Stabilize the structure of material, then with modified Li2MnO3Based on material, prepare lithium-rich oxide anode material, suppression
Structural transformation in cyclic process for the prepared lithium-rich oxide anode material, thus effectively reduce material and exist
Oxygen amount of precipitation during initial charge, improves the first charge-discharge efficiency of material, reduces material in cyclic process
Voltage drop, improves the circulation volume conservation rate of material；This material preparation process controllability is good, extensive low cost of manufacture
Honest and clean, process repeatability is high, lot stability is good, is suitable to large-scale production, can meet on market to high voltage, height ratio capacity lithium
The demand of ion battery positive electrode.
Brief description
Fig. 1 is the lithium-rich oxide anode material Li [Li of embodiment 1 preparation0.28Ni0.06Fe0.04Mn0.62]O2(x=
1/12, M=Fe, y=0.02) SEM figure.
Fig. 2 is the lithium-rich oxide anode material Li [Li of embodiment 1 preparation0.28Ni0.06Fe0.04Mn0.62]O2(x=
1/12, M=Fe, y=0.02) cycle performance figure.
Fig. 3 is the lithium-rich oxide anode material Li [Li of embodiment 2 preparation0.2Ni0.1Co0.2Mn0.5]O2(x=1/
5, M=Co, y=0.1) SEM figure.
Fig. 4 is the lithium-rich oxide anode material Li [Li of embodiment 2 preparation0.2Ni0.1Co0.2Mn0.5]O2(x=1/
5, M=Co, y=0.1) cycle performance figure.
Fig. 5 is the lithium-rich oxide anode material Li [Li of embodiment 3 preparation0.11Ni0.28Al0.1Mn0.51]O2(x=
1/3, M=Al, y=0.05) SEM figure.
Fig. 6 is the lithium-rich oxide anode material Li [Li of embodiment 3 preparation0.11Ni0.28Al0.1Mn0.51]O2(x=
1/3, M=Al, y=0.05) cycle performance figure.
Fig. 7 is the lithium-rich oxide anode material Li [Li of embodiment 4 preparation0.03Ni0.43Cr0.04Mn0.50]O2(x=
9/20, M=Cr, y=0.02) SEM figure.
Fig. 8 is the lithium-rich oxide anode material Li [Li of embodiment 4 preparation0.03Ni0.43Cr0.04Mn0.50]O2(x=
9/20, M=Cr, y=0.02) cycle performance figure.
Specific embodiment
Tell about the detailed process of the present invention by the following examples, the convenience that embodiment is to understand is provided, rather than
Limit the present invention.
Embodiment 1：
A kind of preparation method of lithium-rich oxide anode material, the chemistry of described lithium-rich oxide anode material
Molecular formula is Li [Li0.28Ni0.06Fe0.04Mn0.62]O2(x=1/12, M=Fe, y=0.02), its preparation methods steps are as follows：
1) weigh 87.14g MnSO4·H2O and 16.16g Fe (NO3)3·9H2O preparing metal ion concentration is 1mol/L
Solution；
2) in above-mentioned solution, under the conditions of continuously stirred, it is slowly added to the mixed solution of ammonia and sodium carbonate, mixing is molten
In liquid, ammonia concn is 0.2mol/L, and concentration of sodium carbonate is 2mol/L, to control reacting liquid pH value to be 10, carries out precipitation,
Precipitate is filtered, washed and dried, obtains the MnCO of Fe doping3Material；
3) weigh 41.05g Li2CO3, and by it with step 2) MnCO of Fe doping that obtains3Material is mixed evenly, and is placed in
Carry out roasting in Muffle furnace, sintering temperature is 400 DEG C, roasting time is 80h, obtain the Li of Fe doping2MnO3Material；
4) by 17.00gCH3COOLi·2H2O、18.42g Ni(NO3)2·6H2O and 25.33g Mn (CH3COO)2·4H2O
Mixing, obtains mixed solution, and metal ion total concentration is 2mol/L, by step 3) Li of the Fe that obtains doping2MnO3Material is put into
Obtain suspension in mixed solution, under conditions of stirring, suspension is evaporated, obtains persursor material；
5) by step 4) persursor material that obtains is placed in Muffle furnace and carries out roasting, and sintering temperature is 950 DEG C, during roasting
Between be 5h, obtain 80.70g lithium-rich oxide anode material Li [Li0.28Ni0.08Mn0.64]O2.
Fig. 1 is the lithium-rich oxide anode material Li [Li of embodiment 1 preparation0.28Ni0.06Fe0.04Mn0.62]O2SEM
Figure.
Prepared lithium-rich oxide anode material is used for preparing the positive electrode of height ratio capacity lithium ion battery.
Fig. 2 is the lithium-rich oxide anode material Li [Li of embodiment 1 preparation0.28Ni0.06Fe0.04Mn0.62]O2Assembling
Become the cycle performance figure of button cell.In figure shows using the Li [Li prepared by this method0.28Ni0.06Fe0.04Mn0.62]O2Material
There is higher specific discharge capacity and good cycle performance.
Embodiment 2：
A kind of preparation method of lithium-rich oxide anode material, the chemistry of described lithium-rich oxide anode material
Molecular formula is Li [Li0.2Ni0.1Co0.2Mn0.5]O2(x=1/5, M=Co, y=0.1), its preparation methods steps are as follows：
1) weigh 27.58g LiNO respectively3·H2O,22.99gMnCO3And 16.05gCo3O4, mix homogeneously；
2) by step 1) mixture of gained is placed in Muffle furnace and carries out roasting, and sintering temperature is 750 DEG C, and roasting time is
5h, obtains the Li of Co doping2MnO3Material；
3) prepare 42.78g NiCl 6H2O and 50.71g MnSO4·4H2The mixed solution of O, metal ion total concentration is
2.5mol/L；
4) under the conditions of continuously stirred, to step 3) it is slowly added to ammonia in the solution of gained and the mixing of sodium hydroxide is molten
Liquid, in mixed solution, ammonia concn is 0.3mol/L, and concentration of sodium carbonate is 4mol/L, to control reacting liquid pH value to be 10, carry out
Precipitation, obtains the mixed sediment of nickel hydroxide and manganous hydroxide, mixed sediment is filtered, washed and dried；
5) by step 2) Li of the Co of gained doping2MnO3Material, step 4) gained mixed sediment, and
27.58gLiNO3 mix homogeneously, is placed in Muffle furnace and carries out roasting, and sintering temperature is 850 DEG C, and roasting time is 10h, obtains
85.45g lithium-rich oxide anode material Li [Li0.2Ni0.1Co0.2Mn0.5]O2.
Fig. 3 is the lithium-rich oxide anode material Li [Li of embodiment 2 preparation0.2Ni0.1Co0.2Mn0.5]O2SEM
Figure.
Prepared lithium-rich oxide anode material is used for preparing the positive electrode of height ratio capacity lithium ion battery.
Fig. 4 is the lithium-rich oxide anode material Li [Li of embodiment 2 preparation0.2Ni0.1Co0.2Mn0.5]O2It is assembled into
The cycle performance figure of button cell.In figure shows with the Li [Li prepared by this method0.2Ni0.1Co0.2Mn0.5]O2Material has relatively
High specific discharge capacity and good cycle performance.
Embodiment 3：
A kind of preparation method of lithium-rich oxide anode material, the chemistry of described lithium-rich oxide anode material
Molecular formula is Li [Li0.11Ni0.28Al0.1Mn0.51]O2(x=1/3, M=Al, y=0.05), its preparation methods steps are as follows：
1) 9.32g LiOH, 10.87gMn (OH) are weighed respectively2With 37.51gAl (NO3)3·9H2O, mix homogeneously；
2) by step 1) mixture of gained is placed in Muffle furnace and carries out roasting, and sintering temperature is 550 DEG C, and roasting time is
55h, obtains the Li of Al doping2MnO3Material；
3) by step 2) Li of the Al that obtains doping2MnO3Material and 24.63g Li2CO3, 10.21gNiO and
44.06gMnCO3 mix homogeneously, obtains mixture；
4) by step 3) the mixture thing of gained is placed in Muffle furnace and carries out roasting, and sintering temperature is 700 DEG C, roasting time
For 15h, obtain 86.85g lithium-rich oxide anode material Li [Li0.11Ni0.28Al0.1Mn0.51]O2.
Fig. 5 is the lithium-rich oxide anode material Li [Li of embodiment 2 preparation0.11Ni0.28Al0.1Mn0.51]O2SEM
Figure.
Prepared lithium-rich oxide anode material is used for preparing the positive electrode of height ratio capacity lithium ion battery.
Fig. 6 is the lithium-rich oxide anode material Li [Li of embodiment 2 preparation0.11Ni0.28Al0.1Mn0.51]O2Assembling
Become the cycle performance figure of button cell.In figure shows with the Li [Li prepared by this method0.11Ni0.28Al0.1Mn0.51]O2Material has
There are higher specific discharge capacity and good cycle performance.
Embodiment 4：
A kind of preparation method of lithium-rich oxide anode material, the chemistry of described lithium-rich oxide anode material
Molecular formula is Li [Li0.03Ni0.43Cr0.04Mn0.50]O2(x=9/20, M=Cr, y=0.02), its preparation methods steps are as follows：
1) weigh 4.93g Li respectively2CO3,3.07gMnCO3With 16.01gCr (NO3)3·9H2O, mix homogeneously；
2) by step 1) mixing material of gained is placed in Muffle furnace and carries out roasting, and sintering temperature is 650 DEG C, roasting time
For 25h, obtain the Li of Cr doping2MnO3Material；
3) by step 2) Li of the Cr that obtains doping2MnO3Material and 37.76gLiOH, 51.04gNiCO3With
54.03gMnCO3Mix homogeneously, is placed in Muffle furnace carrying out roasting, and sintering temperature is 800 DEG C, and roasting time is 12h, obtains
93.94g lithium-rich oxide anode material Li [Li0.03Ni0.43Cr0.04Mn0.50]O2.
Fig. 7 is the lithium-rich oxide anode material Li [Li of embodiment 4 preparation0.03Ni0.43Cr0.04Mn0.50]O2SEM
Figure.
Prepared lithium-rich oxide anode material is used for preparing the positive electrode of height ratio capacity lithium ion battery.
Fig. 8 is the lithium-rich oxide anode material Li [Li of embodiment 4 preparation0.03Ni0.43Cr0.04Mn0.50]O2Assembling
Become the cycle performance figure of button cell.In figure shows prepared Li [Li0.03Ni0.43Cr0.04Mn0.50]O2Material has higher
Specific discharge capacity and good cycle performance.
In sum, the lithium-rich oxide of the method preparation reduces the voltage attenuation of material, improves material
Cycle performance.Therefore, the lithium-rich oxide anode material of the method preparation is hopeful meet on market to high-performance lithium
The demand to height ratio capacity and Width funtion window positive electrode for the ion battery.
Although invention has been described for above-mentioned application example, the invention is not limited in above-mentioned being embodied as
Mode, above-mentioned specific embodiment is only schematically, rather than restricted, and those of ordinary skill in the art is at this
Under the enlightenment of invention, without deviating from the spirit of the invention, many variations can also be made, these belong to the present invention's
Within protection.
Claims (4)
1. a kind of preparation method of lithium-rich oxide anode material it is characterised in that：Described lithium-rich oxide anode
The chemical molecular formula of material is Li [Li(1-2x)/3Nix-yM2yMn2/3-x/3-y]O2, in formula：0<x<0.5,0<y<X, M are Fe, Co, Al
Mixture with one of Cr or two or more arbitrary proportion；
Its preparation methods steps are as follows：
1) by Li source, Mn source and M source metal mix homogeneously, obtain mixture；
2) by said mixture under conditions of 400-750 DEG C roasting 5-80h, obtain the metal-doped Li of M2MnO3Material；
3) by Li metal-doped for above-mentioned M2MnO3Material is sufficiently mixed uniformly with Li source, Ni source and Mn source, obtains mixing material；
4) by above-mentioned mixing material at 700-950 DEG C roasting 5-15h；
5) it is cooled to room temperature, obtain lithium-rich oxide anode material Li [Li(1-2x)/3Nix-yM2yMn2/3-x/3-y]O2.
2. according to claim 1 lithium-rich oxide anode material preparation method it is characterised in that：Described step 1)
Middle Li source is the mixture of one of lithium carbonate, Lithium hydrate, lithium nitrate and Quilonorm (SKB) or two or more arbitrary proportion；Mn source
For aoxidizing two or more of one of (sub-) manganese, hydroxide (sub-) manganese, hydroxyl oxidize manganese, manganese carbonate, manganese nitrate and manganese acetate
The mixture of meaning ratio；M source metal be one of the carbonate of M metal, hydroxide, nitrate and acetate or two kinds with
The mixture of upper arbitrary proportion；The mol ratio in Li source, Mn source and M source metal is (2-4x):(1-2x-3y):3y, in formula：0<x<
0.5,0<y<x.
3. according to claim 1 lithium-rich oxide anode material preparation method it is characterised in that：Described step 3)
Middle Li source is the mixture of one of lithium carbonate, Lithium hydrate, lithium nitrate and Quilonorm (SKB) or two or more arbitrary proportion；Ni source
For one of oxidation (sub-) nickel, hydroxide (sub-) nickel, hydroxy nickel oxide, nickelous carbonate, nickel nitrate and nickel acetate or two or more
The mixture of arbitrary proportion；Mn source is oxidation (sub-) manganese, hydroxide (sub-) manganese, hydroxyl oxidize manganese, manganese carbonate, manganese nitrate and acetic acid
The mixture of the two or more arbitrary proportion of one of manganese；The metal-doped Li of M2MnO3Material is with Li, Ni and the Mn's being added
Mol ratio is (1-2x)：3x:(3x-3y)/2:(3x+3y)/2, in formula：0<x<0.5,0<y<x.
4. a kind of application of lithium-rich oxide anode material as claimed in claim 1 it is characterised in that：For preparing high ratio
The positive electrode of capacity lithium ion battery.
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