CN102646825A - Lithium nickel manganese oxygen materials, preparing method thereof and lithium ion batteries containing same - Google Patents
Lithium nickel manganese oxygen materials, preparing method thereof and lithium ion batteries containing same Download PDFInfo
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- CN102646825A CN102646825A CN2012101424223A CN201210142422A CN102646825A CN 102646825 A CN102646825 A CN 102646825A CN 2012101424223 A CN2012101424223 A CN 2012101424223A CN 201210142422 A CN201210142422 A CN 201210142422A CN 102646825 A CN102646825 A CN 102646825A
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- nickel
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- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- OGCCXYAKZKSSGZ-UHFFFAOYSA-N [Ni]=O.[Mn].[Li] Chemical compound [Ni]=O.[Mn].[Li] OGCCXYAKZKSSGZ-UHFFFAOYSA-N 0.000 title abstract 7
- 238000002360 preparation method Methods 0.000 claims abstract description 49
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 14
- 238000000975 co-precipitation Methods 0.000 claims abstract description 11
- 229910006703 Li—Ni—Mn—O Inorganic materials 0.000 claims description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- 239000011572 manganese Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 24
- 229910016757 Ni0.5Mn1.5(OH)4 Inorganic materials 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000002927 oxygen compounds Chemical class 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 239000008247 solid mixture Substances 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 230000003750 conditioning effect Effects 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 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
- 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 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 11
- 238000007781 pre-processing Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 17
- 239000011259 mixed solution Substances 0.000 description 10
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 8
- -1 compound carbonate Chemical class 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
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- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides lithium nickel manganese oxygen materials, a preparing method thereof and lithium ion batteries containing the same, belongs to the technical field of lithium ion batteries, and is capable of solving the problems of low specific capacity and cycle performance of existing lithium nickel manganese oxygen materials and lithium ion batteries prepared by the materials. The preparing method of the lithium nickel manganese oxygen materials comprises a coprecipitation preparation of nickel manganese compound step, a precursor preprocessing step and a solid phase synthesis step. According to the lithium nickel manganese oxygen materials, the preparing method thereof and the lithium ion batteries containing the same, nickel manganese compounds with good performances are obtained by selecting appropriate technological parameters and preprocessed at a high temperature, so that the specific capacity and the cycle performance of lithium ion batteries are improved greatly. The lithium nickel manganese oxygen materials are prepared through the method, and the lithium ion batteries comprise the lithium nickel manganese oxygen materials.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of Li-Ni-Mn-O material and preparation method thereof, contain the lithium ion battery of this material.
Background technology
In recent years, along with the requirement of the increasingly serious of the energy, environmental problem and electronic product lightness, the scientific research personnel deepens continuously to the research of lithium ion battery.Because business-like anode material for lithium-ion batteries LiCoO
2Price is high, toxic, and the scientific research personnel strives to find its substitute always.LiMn2O4 receives much attention owing to it is cheap, nontoxic.And contain the LiNi of nickel
0.5Mn
1.5O
4The platform that mainly has 4.7V in the charge and discharge process, corresponding Ni
2+/ Ni
4+The OR process, also have minimum 4V platform, corresponding to Mn
3+/ Mn
4+The OR process.Because LiNi
0.5Mn
1.5O
4Theoretical specific capacity can reach 146.7mAh/g, be hopeful as power battery material, become the focus of current lithium ion battery material research.
Present LiNi
0.5Mn
1.5O
4Preparation methods has a variety of, mainly contains solid phase method, coprecipitation, co-precipitation-solid-phase synthesis, compound carbonate method, sol-gel process, molten salt growth method, emulsion seasoning and ullrasonic spraying high-temperature decomposition etc.
In co-precipitation-solid-phase synthesis, co-precipitation is through precipitation reagent nickel presoma, manganese presoma to be changed into co-precipitation nickel manganese compound, for example Ni
0.5Mn
1.5(CO
3)
2, Ni
0.5Mn
1.5(OH)
4Deng; The factor that influences the generation of nickel manganese compound in this process is a lot; For example: the pH value of the selection of reactant, the selection of precipitation reagent, course of reaction; And the high temperature preliminary treatment of nickel manganese compound etc., these treatment process are very crucial to the good nickel manganese compound of obtained performance, and finally have influence on the performance of electrode material.The processing of raw material in the solid phase synthesis step, for example: the mixing uniformity in nickel manganese compound and lithium source, and the control of sintering process also is the key factor of influence preparation electrode material cycle performance.
One Chinese patent application number: CN201010045604.X, a kind of 5V anode material for lithium-ion batteries LiNi
0.5Mn
1.5O
4Synthetic method, adopt the synthetic LiNi of oxalate coprecipitation-solid-phase synthesis
0.5Mn
1.5O
4Material, the 0.1C rate charge-discharge, specific capacity is about 130mAh/g first.
The present invention is through choosing the nickel manganese compound that appropriate parameters has obtained function admirable; And nickel manganese compound carried out the high temperature preliminary treatment; Obtained the Li-Ni-Mn-O material of better performances, thereby made the Li-Ni-Mn-O material and obtain bigger raising by the specific capacity and the cycle performance of the lithium ion battery of its preparation.
Summary of the invention
The objective of the invention is to solve Li-Ni-Mn-O material that existing co-precipitation-solid-phase synthesis makes and, a kind of preparation method of lithium ion battery material is provided by the specific capacity and the low problem of cycle performance of the lithium ion battery of its preparation.
Solving the technical scheme that technical problem of the present invention adopted is a kind of Li-Ni-Mn-O preparation methods, comprising:
1) prepared by co-precipitation nickel manganese compound step:
Mixture aqueous solution in amount of substance ratio Ni ︰ Mn=1 ︰ 3 preparation nickel presomas and manganese presoma adds alkaline pH value conditioning agent in mixture aqueous solution, the pH value is controlled at 10.1 ~ 10.5, obtains presoma Ni
0.5Mn
1.5(OH)
4
2) presoma Ni
0.5Mn
1.5(OH)
4Pre-treatment step:
With said presoma Ni
0.5Mn
1.5(OH)
4Programming rate with 1 ~ 10 ℃/min is heated to 400 ~ 600 ℃, and insulation 2 ~ 12h carries out preliminary treatment; Obtain the nickel manganese and oxygen compound; In amount of substance ratio Li ︰ Ni ︰ Mn=1.05～1.02 ︰, 0.5 ︰ 1.5 lithium source and nickel manganese and oxygen compound batch mixing are got solid mixture, pulverize, get crushed mixture;
3) solid phase synthesis step:
With step 2) crushed mixture of gained is dry, and sintering under oxygen-containing atmosphere is heated to 800 ~ 950 ℃, calcining 2 ~ 24h with the programming rate of 0.5 ~ 10 ℃/min; Reduce to 500 ~ 700 ℃ with the cooling rate of 0.5 ~ 10 ℃/min again, annealing 2 ~ 24h is cooled to room temperature at last naturally, promptly obtains the Li-Ni-Mn-O material.
Preferably, described pulverizing is ball mill grinding or grinds.
Further preferably, described ball mill grinding is a wet ball grinding, and said wet ball grinding comprises: with ethanol and the solid mixture mixed by 1 ︰ (1 ~ 1.3) mL/g, with rotating speed ball milling 1 ~ 12h of 300 ~ 650r/min.
Preferably, described nickel presoma is any one or a few in nickel nitrate, nickel acetate, nickelous sulfate, the nickel chloride.
Preferably, described manganese presoma is any one or a few in manganese nitrate, manganese acetate, manganese sulfate, the manganese chloride.
Preferably, described lithium source is any one or a few in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, the lithia.
Preferably, described alkaline pH value conditioning agent is NaOH solution or KOH solution.
Technical problem to be solved by this invention also comprises, to existing Li-Ni-Mn-O material specific capacity, the low problem of cycle performance, a kind of specific capacity, the good Li-Ni-Mn-O material of cycle performance is provided.
Solving the technical scheme that technical problem of the present invention adopted is a kind of Li-Ni-Mn-O material, and it is through method for preparing.
Because Li-Ni-Mn-O material of the present invention is through method for preparing, its specific capacity, cycle performance are better.
Technical problem to be solved by this invention also comprises, to the existing low problem of lithium ion battery specific capacity, cycle performance by the Li-Ni-Mn-O material preparation, a kind of specific capacity, the good lithium ion battery of cycle performance is provided.
Solving the technical scheme that technical problem of the present invention adopted is a kind of lithium ion battery, and its positive pole contains above-mentioned Li-Ni-Mn-O material.
Because the positive pole of lithium ion battery of the present invention contains above-mentioned Li-Ni-Mn-O material, so its specific capacity, cycle performance are better.
Description of drawings
Fig. 1 is the XRD figure spectrum of the prepared Li-Ni-Mn-O material of the embodiment of the invention.
Fig. 2 is the discharge cycles performance curve of the prepared Li-Ni-Mn-O material of the embodiment of the invention.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, the present invention is described in further detail below in conjunction with accompanying drawing and embodiment.
Embodiment 1:
Present embodiment provides a kind of Li-Ni-Mn-O preparation methods:
Mixture aqueous solution in amount of substance ratio Ni ︰ Mn=1 ︰ 3 preparation nickel chlorides and nickel nitrate (both amount of substance ratios are 1 ︰ 1), manganese nitrate; Under stirring; To the mixed solution and dripping molar concentration is the NaOH solution of 2M; The pH value of mixed solution is controlled at about 10.3, to guarantee Ni
2+, Mn
2+Deposition fully, leave standstill 2h after, suction filtration, three times, 110 ℃ dry 12h of washing obtain precursor Ni
0.5Mn
1.5(OH)
4
Step 2. presoma Ni
0.5Mn
1.5(OH)
4Preliminary treatment
The precursor Ni that step 1 is obtained
0.5Mn
1.5(OH)
4Programming rate with 6 ℃/min is heated to 600 ℃, reduces to room temperature naturally behind the insulation 2h, obtains the nickel manganese and oxygen compound; In amount of substance ratio Li ︰ Ni ︰ Mn=1.04 ︰ 0.5 ︰ 1.5 lithium nitrate and nickel manganese and oxygen compound batch mixing are got solid mixture, wherein Li is excessive a little is in order to remedy a small amount of volatilization loss of lithium in the follow-up pyroprocess; Ratio in ethanol and solid mixture is that 1.3mL/g adds ball mill again, with the rotating speed ball milling 2h of 650r/min, gets crushed mixture.
Step 3. solid phase synthesis
The crushed mixture that step 2 is obtained is dry, and sintering under air atmosphere is heated to 900 ℃, calcining 24h with the programming rate of 10 ℃/min; Reduce to 500 ℃ with the cooling rate of 10 ℃/min again, annealing 24h is cooled to room temperature at last naturally, promptly obtains the Li-Ni-Mn-O material.
Optional, can continue with prepared Li-Ni-Mn-O material preparation Experimental cell with pole piece and test battery.
The preparation experiment battery uses the process of pole piece to be: Li-Ni-Mn-O material and conductive agent acetylene black, binding agent PVDF (Kynoar) are mixed according to mass ratio 8 ︰ 1 ︰ 1, with NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry, evenly be coated on the aluminium foil; Put into baking oven, dry 1h down, take out and be washed into pole piece at 100 ℃; At 85 ℃ of following vacuumize 12h; Carry out compressing tablet,, make Experimental cell and use pole piece at 85 ℃ of following vacuumize 12h.
The process of preparation test battery is: the pole piece with above-mentioned preparation is a positive pole, is to electrode with the lithium sheet, and electrolyte is that concentration is the LiPF of 1.5mol/L
6Solution, its solvent is EC (ethyl carbonate ester)+DMC (dimethyl carbonate), wherein the volume ratio of EC (ethyl carbonate ester) and DMC (dimethyl carbonate) is 1 ︰ 1, electrolyte is that concentration is the LiPF of 1.5mol/L
6EC (ethyl carbonate ester) solution+DMC (dimethyl carbonate) solution; Wherein the volume ratio of EC (ethyl carbonate ester) and DMC (dimethyl carbonate) is 1 ︰ 1; Barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell, and discharging and recharging by voltage is 3.5 ~ 4.9V; Charge and discharge cycles is provided with: the 1st ~ 10 charging and discharging currents is 0.1C, and the 11st ~ 80 charging and discharging currents is 1C (1C=130mA/g).
The discharge cycles test data of the material of present embodiment preparation is seen table 1.
Embodiment 2:
Present embodiment provides a kind of Li-Ni-Mn-O preparation methods:
Mixture aqueous solution in amount of substance ratio Ni ︰ Mn=1 ︰ 3 preparation nickelous sulfate, manganese nitrate and manganese acetates (both amount of substance ratios are 1 ︰ 1); Under stirring; To the mixed solution and dripping molar concentration is the KOH solution of 2M; The pH value of mixed solution is controlled at about 10.1, to guarantee Ni
2+, Mn
2+Deposition fully, leave standstill 2h after, suction filtration, three times, 110 ℃ dry 12h of washing obtain precursor Ni
0.5Mn
1.5(OH)
4
Step 2. presoma Ni
0.5Mn
1.5(OH)
4Preliminary treatment
The precursor Ni that step 1 is obtained
0.5Mn
1.5(OH)
4Programming rate with 10 ℃/min is heated to 400 ℃, reduces to room temperature naturally behind the insulation 6h, obtains the nickel manganese and oxygen compound; In amount of substance ratio Li ︰ Ni ︰ Mn=1.02 ︰ 0.5 ︰ 1.5 lithia and nickel manganese and oxygen compound batch mixing are got solid mixture, wherein Li is excessive a little is in order to remedy a small amount of volatilization loss of lithium in the follow-up pyroprocess; Ratio in ethanol and solid mixture is that 1mL/g adds ball mill again, with the rotating speed ball milling 12h of 450r/min, gets crushed mixture.
Step 3. solid phase synthesis
The crushed mixture that step 2 is obtained is dry, and sintering under pure oxygen atmosphere is heated to 800 ℃, calcining 9h with the programming rate of 0.5 ℃/min; Reduce to 600 ℃ with the cooling rate of 8 ℃/min again, annealing 2h is cooled to room temperature at last naturally, promptly obtains the Li-Ni-Mn-O material.
Optional, can continue with prepared Li-Ni-Mn-O material preparation Experimental cell with pole piece and test battery.
The preparation experiment battery is identical with method among the embodiment 1 with pole piece and test battery method.
The discharge cycles test data of the material of present embodiment preparation is seen table 1.
Embodiment 3:
Present embodiment provides a kind of Li-Ni-Mn-O preparation methods:
In the mixture aqueous solution of amount of substance ratio Ni ︰ Mn=1 ︰ 3 preparation nickel acetates and manganese sulfate, under stirring, be the NaOH solution of 2M to the mixed solution and dripping molar concentration, the pH value of mixed solution is controlled at about 10.5, with assurance Ni
2+, Mn
2+Deposition fully, leave standstill 2h after, suction filtration, three times, 110 ℃ dry 12h of washing obtain precursor Ni
0.5Mn
1.5(OH)
4
Step 2. presoma Ni
0.5Mn
1.5(OH)
4Preliminary treatment
The precursor Ni that step 1 is obtained
0.5Mn
1.5(OH)
4Programming rate with 4 ℃/min is heated to 450 ℃, reduces to room temperature naturally behind the insulation 8h, obtains the nickel manganese and oxygen compound; In amount of substance ratio Li ︰ Ni ︰ Mn=1.05 ︰ 0.5 ︰ 1.5 lithium hydroxide and lithium nitrate (both amount of substance ratios are 1 ︰ 1), nickel manganese and oxygen compound batch mixing are got solid mixture, wherein Li is excessive a little is in order to remedy a small amount of volatilization loss of lithium in the follow-up pyroprocess; Ratio in ethanol and said solid mixture is that 1.2mL/g adds ball mill again, with the rotating speed ball milling 8h of 300r/min, gets crushed mixture.
Step 3. solid phase synthesis
The crushed mixture that step 2 is obtained is dry, and sintering under air atmosphere is heated to 950 ℃, calcining 2h with the programming rate of 8 ℃/min; Reduce to 700 ℃ with the cooling rate of 3 ℃/min again, annealing 10h is cooled to room temperature at last naturally, promptly obtains the Li-Ni-Mn-O material.
Optional, can continue with prepared Li-Ni-Mn-O material preparation Experimental cell with pole piece and test battery.
The preparation experiment battery is identical with method among the embodiment 1 with pole piece and test battery method.
The discharge cycles test data of the material of present embodiment preparation is seen table 1.
Embodiment 4:
Present embodiment provides a kind of Li-Ni-Mn-O preparation methods:
In the mixture aqueous solution of amount of substance ratio Ni ︰ Mn=1 ︰ 3 preparation nickelous sulfates and manganese acetate, under stirring, be the KOH solution of 2M to the mixed solution and dripping molar concentration, the pH value of mixed solution is controlled at about 10.2, with assurance Ni
2+, Mn
2+Deposition fully, leave standstill 2h after, suction filtration, three times, 110 ℃ dry 12h of washing obtain precursor Ni
0.5Mn
1.5(OH)
4
Step 2. presoma Ni
0.5Mn
1.5(OH)
4Preliminary treatment
The precursor Ni that step 1 is obtained
0.5Mn
1.5(OH)
4Programming rate with 1 ℃/min is heated to 550 ℃, reduces to room temperature naturally behind the insulation 10h, obtains the nickel manganese and oxygen compound; In amount of substance ratio Li ︰ Ni ︰ Mn=1.03 ︰ 0.5 ︰ 1.5 lithium carbonate and nickel manganese and oxygen compound batch mixing are got solid mixture, wherein Li is excessive a little is in order to remedy a small amount of volatilization loss of lithium in the follow-up pyroprocess; Ratio in ethanol and said solid mixture is that 1.1mL/g adds ball mill again, with the rotating speed ball milling 1h of 400r/min, gets crushed mixture.
Step 3. solid phase synthesis
The crushed mixture that step 2 is obtained is dry, and sintering under pure oxygen atmosphere is heated to 820 ℃, calcining 19h with the programming rate of 2 ℃/min; Reduce to 650 ℃ with the cooling rate of 0.5 ℃/min again, annealing 20h is cooled to room temperature at last naturally, promptly obtains the Li-Ni-Mn-O material.
Optional, can continue with prepared Li-Ni-Mn-O material preparation Experimental cell with pole piece and test battery.
The preparation experiment battery is identical with method among the embodiment 1 with pole piece and test battery method.
Embodiment 5:
Present embodiment provides a kind of Li-Ni-Mn-O preparation methods:
In the mixture aqueous solution of amount of substance ratio Ni ︰ Mn=1 ︰ 3 preparation nickel nitrates and manganese chloride, under stirring, be the NaOH solution of 2M to the mixed solution and dripping molar concentration, the pH value of mixed solution is controlled at about 10.4, with assurance Ni
2+, Mn
2+Deposition fully, leave standstill 2h after, suction filtration, three times, 110 ℃ dry 12h of washing obtain precursor Ni
0.5Mn
1.5(OH)
4
Step 2. presoma Ni
0.5Mn
1.5(OH)
4Preliminary treatment
The precursor Ni that step 1 is obtained
0.5Mn
1.5(OH)
4Programming rate with 8 ℃/min is heated to 500 ℃, reduces to room temperature naturally behind the insulation 12h, obtains the nickel manganese and oxygen compound; In amount of substance ratio Li ︰ Ni ︰ Mn=1.02 ︰ 0.5 ︰ 1.5 lithium acetate and nickel manganese and oxygen compound batch mixing are got solid mixture, wherein Li is excessive a little is in order to remedy a small amount of volatilization loss of lithium in the follow-up pyroprocess, to grind, getting crushed mixture.
Step 3. solid phase synthesis
The crushed mixture that step 2 is obtained is dry, and sintering under air atmosphere is heated to 850 ℃, calcining 11h with the programming rate of 5 ℃/min; Reduce to 550 ℃ with the cooling rate of 5 ℃/min again, annealing 8h is cooled to room temperature at last naturally, promptly obtains the Li-Ni-Mn-O material.
Optional, can continue with prepared Li-Ni-Mn-O material preparation Experimental cell with pole piece and test battery.
The preparation experiment battery is identical with method among the embodiment 1 with pole piece and test battery method.
The discharge cycles test data of the material of present embodiment preparation is seen table 1.
As shown in Figure 1, the XRD test result of the Li-Ni-Mn-O material of present embodiment preparation shows that this material is spinel-type LiNi
0.5Mn
1.5O
4, diffraction maximum is sharp-pointed, and intensity is big, the free from admixture peak, this material crystal formation is intact.
As shown in Figure 2, specific capacity, the cycle performance of the Li-Ni-Mn-O material of present embodiment preparation are good.
The discharge cycles test data of the Li-Ni-Mn-O material that the embodiment of the invention is prepared is seen table 1, can know from this table, and the specific capacity of this material is high, cycle performance is good.
The discharge cycles test data table of the Li-Ni-Mn-O material that table 1 embodiment is prepared
Obviously, the preparation method of above-mentioned each embodiment also can carry out many known variations; For example: other known compound also can be selected in nickel presoma, manganese presoma, lithium source; Pulverize also can adopt except that grind with ball mill grinding other known manner carry out; Ball mill grinding can be the wet-milling of use other ball milling agent except that ethanol; Alkaline pH value conditioning agent is other the known reagent that can realize the object of the invention except that NaOH solution or KOH solution.
Embodiment 6:
It is a kind of by method for preparing Li-Ni-Mn-O material that present embodiment provides.
Embodiment 7:
The lithium ion battery that present embodiment provides a kind of positive pole to contain above-mentioned Li-Ni-Mn-O material, this lithium ion battery for example also comprises other necessary assembly certainly, negative pole, barrier film, electrolyte and shell etc. repeat no more here.
It is understandable that above execution mode only is the illustrative embodiments that adopts for principle of the present invention is described, yet the present invention is not limited thereto.For the one of ordinary skilled in the art, under the situation that does not break away from spirit of the present invention and essence, can make various modification and improvement, these modification also are regarded as protection scope of the present invention with improving.
Claims (9)
1. a Li-Ni-Mn-O preparation methods is characterized in that, comprising:
1) prepared by co-precipitation nickel manganese compound step:
Mixture aqueous solution in amount of substance ratio Ni ︰ Mn=1 ︰ 3 preparation nickel presomas and manganese presoma adds alkaline pH value conditioning agent in mixture aqueous solution, the pH value is controlled at 10.1 ~ 10.5, obtains presoma Ni
0.5Mn
1.5(OH)
4
2) presoma Ni
0.5Mn
1.5(OH)
4Pre-treatment step:
With said presoma Ni
0.5Mn
1.5(OH)
4Programming rate with 1 ~ 10 ℃/min is heated to 400 ~ 600 ℃, and insulation 2 ~ 12h carries out preliminary treatment; Obtain the nickel manganese and oxygen compound; In amount of substance ratio Li ︰ Ni ︰ Mn=1.05～1.02 ︰, 0.5 ︰ 1.5 lithium source and nickel manganese and oxygen compound batch mixing are got solid mixture, pulverize, get crushed mixture;
3) solid phase synthesis step:
With step 2) crushed mixture of gained is dry, and sintering under oxygen-containing atmosphere is heated to 800 ~ 950 ℃, calcining 2 ~ 24h with the programming rate of 0.5 ~ 10 ℃/min; Reduce to 500 ~ 700 ℃ with the cooling rate of 0.5 ~ 10 ℃/min again, annealing 2 ~ 24h is cooled to room temperature at last naturally, promptly obtains the Li-Ni-Mn-O material.
2. Li-Ni-Mn-O preparation methods as claimed in claim 1 is characterized in that, described pulverizing is ball mill grinding or grinds.
3. Li-Ni-Mn-O preparation methods as claimed in claim 2; It is characterized in that; Described ball mill grinding is a wet ball grinding, and said wet ball grinding comprises: with ethanol and the solid mixture mixed by 1 ︰ (1 ~ 1.3) mL/g, with rotating speed ball milling 1 ~ 12h of 300 ~ 650r/min.
4. like any described Li-Ni-Mn-O preparation methods in the claim 1 ~ 3, it is characterized in that described nickel presoma is any one or a few in nickel nitrate, nickel acetate, nickelous sulfate, the nickel chloride.
5. like any described Li-Ni-Mn-O preparation methods in the claim 1 ~ 3, it is characterized in that described manganese presoma is any one or a few in manganese nitrate, manganese acetate, manganese sulfate, the manganese chloride.
6. like any described Li-Ni-Mn-O preparation methods in the claim 1 ~ 3, it is characterized in that described lithium source is any one or a few in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, the lithia.
7. like any described Li-Ni-Mn-O preparation methods in the claim 1 ~ 3, it is characterized in that described alkaline pH value conditioning agent is NaOH solution or KOH solution.
8. a Li-Ni-Mn-O material is characterized in that, it is through any described method preparation in the claim 1 to 7.
9. a lithium ion battery is characterized in that, its positive pole contains the described Li-Ni-Mn-O material of claim 8.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103311525A (en) * | 2013-06-08 | 2013-09-18 | 深圳华粤宝电池有限公司 | Preparation method of positive material of lithium-ion battery |
| CN104868117A (en) * | 2015-05-11 | 2015-08-26 | 合肥国轩高科动力能源股份公司 | Modified preparation method for lithium manganate anode material of lithium-ion battery |
| CN105206822A (en) * | 2015-07-29 | 2015-12-30 | 上海电气集团股份有限公司 | Method for synthesizing lithium ion battery high-potential positive electrode material |
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|---|---|---|---|---|
| CN102034967A (en) * | 2010-11-09 | 2011-04-27 | 中国海洋石油总公司 | Coprecipitation preparation method of nickel manganese lithium oxide of anode material of high-voltage lithium battery |
| CN102324513A (en) * | 2011-09-19 | 2012-01-18 | 奇瑞汽车股份有限公司 | Lithium nickel manganese oxygen composite cathode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102034967A (en) * | 2010-11-09 | 2011-04-27 | 中国海洋石油总公司 | Coprecipitation preparation method of nickel manganese lithium oxide of anode material of high-voltage lithium battery |
| CN102324513A (en) * | 2011-09-19 | 2012-01-18 | 奇瑞汽车股份有限公司 | Lithium nickel manganese oxygen composite cathode material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103311525A (en) * | 2013-06-08 | 2013-09-18 | 深圳华粤宝电池有限公司 | Preparation method of positive material of lithium-ion battery |
| CN103311525B (en) * | 2013-06-08 | 2015-06-24 | 深圳华粤宝电池有限公司 | Preparation method of positive material of lithium-ion battery |
| CN104868117A (en) * | 2015-05-11 | 2015-08-26 | 合肥国轩高科动力能源股份公司 | Modified preparation method for lithium manganate anode material of lithium-ion battery |
| CN105206822A (en) * | 2015-07-29 | 2015-12-30 | 上海电气集团股份有限公司 | Method for synthesizing lithium ion battery high-potential positive electrode material |
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