CN1686926A - Method for preparing laminar oxide material of lithium, cobalt, nickel and manganese through solid phase reaction in low heat - Google Patents
Method for preparing laminar oxide material of lithium, cobalt, nickel and manganese through solid phase reaction in low heat Download PDFInfo
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- CN1686926A CN1686926A CNA2005100116761A CN200510011676A CN1686926A CN 1686926 A CN1686926 A CN 1686926A CN A2005100116761 A CNA2005100116761 A CN A2005100116761A CN 200510011676 A CN200510011676 A CN 200510011676A CN 1686926 A CN1686926 A CN 1686926A
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000003746 solid phase reaction Methods 0.000 title claims abstract description 13
- 239000011572 manganese Substances 0.000 title claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 27
- 229910052748 manganese Inorganic materials 0.000 title abstract description 7
- 229910052759 nickel Inorganic materials 0.000 title abstract description 5
- 229910052744 lithium Inorganic materials 0.000 title description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title description 4
- 229910017052 cobalt Inorganic materials 0.000 title description 2
- 239000010941 cobalt Substances 0.000 title description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title description 2
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910012735 LiCo1/3Ni1/3Mn1/3O2 Inorganic materials 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- 229910013733 LiCo Inorganic materials 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- 206010037660 Pyrexia Diseases 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract 3
- 229910012652 LiCo1 Inorganic materials 0.000 abstract 1
- 150000001242 acetic acid derivatives Chemical class 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 10
- 238000009413 insulation Methods 0.000 description 10
- 238000010792 warming Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000010671 solid-state reaction Methods 0.000 description 4
- 229910014689 LiMnO Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 235000011837 pasties Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910003548 Li(Ni,Co,Mn)O2 Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [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
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910006290 γ-MnOOH Inorganic materials 0.000 description 1
Images
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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)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a method for preparing LiCo1/3Ni1/3Mn1/3O2 material by adopting low-temperature solid-phase reaction, belonging to the field of lithium ion cell position electrode material preparation technology. Said invention utilizes two-step process to prepare precursor body, first step includes the following steps: uniformly mixing LiOH.H2O and H2C2O4 according to mixing ratio of 1:0.8-1.2; uniformly mixing acetates of Co, Ni and Mn according to the ratio of 1:1:1; and second step includes the following steps: ball-grinding and mixing the above-mentioned two materials, vacuum drying at 120-150 deg.C so as to obtain precursor body, roasting said precursor body for 6-15 hr at 500-800 deg.C so as to obtain finall product LiCo1/2Ni1/3Mn1/3O2.
Description
Technical field
The invention belongs to the anode material for lithium-ion batteries preparing technical field, particularly provide a kind of employing low fever solid phase reaction to prepare LiCo
1-2x-yNi
xMn
xM
yO
2The method of material, M is a metal, is used as anode material for lithium-ion batteries.
Technical background
In recent years, round the environmental protection in city and the research and development of power truck, for security and the price problem that solves lithium ion battery, people are carrying out the exploratory development of novel material always.And be widely used in the positive electrode material LiCoO of commodity lithium ion battery at present
2, because this material cost height overcharges unstable the reaching of status architecture and has certain safe new problem at the state of overcharging, so seek the main direction that the anodal equivalent material of super quality and competitive price becomes following lithium ion battery development.Stratiform LiMnO
2Have nontoxic, low-cost, energy density and theoretical capacity advantages of higher, the positive electrode material that is considered to have most development potentiality.But the synthesis condition harshness has limited its practical application.LiMnO
2Be a kind of metastable phase, structural instability in the electrochemistry working cycle changes spinel-like structural into when initial charge, and this transition process is irreversible.To the stratiform manganese behind its doping vario-property is that derivative has synthetic simple, low cost and other advantages, has caused that numerous scholars pay close attention to, and its application prospect is very good.Stratiform Li (Ni, Co, Mn) O
2In the material, by the Li (Ni of Ohzuku and Makimura proposition
1/3Co
1/3Mn
1/3) O
2Material, because its capacity height, the loop attenuation amount is little, can remedy LiCoO
2And LiMnO
2Deficiency, become and had most at present one of new type lithium ion battery positive electrode material of development prospect (T.Ohzuku, Y.Makimura, Chem.Lett.7 (2001): 642-643).
Present Li (Ni, Co, Mn) O
2The synthetic method of material adopts liquid-phase coprecipitation and high temperature solid-state method to synthesize substantially.Traditional high temperature solid state reaction synthesis temperature height, the time is long.As people (De-ChengLi, Takahisa Muta, Lian-Qi Zhang, et al.Effect of synthesis method on theelectrochemical performance of LiNi such as De-Cheng Li
1/3Co
1/3Mn
1/3O
2.Journal of Power Sources, 132 (2004): the 150-155) preparation method of employing solid phase synthesis, the acetate and the lithium acetate of cobalt nickel manganese are pressed stoichiometric, burn 400 ℃ after mixing in advance and obtain presoma, presoma is obtained Li (Ni at 900 ℃ of sintering 20h
1/3Co
13Mn
1/3) O
2Material.People (Jung-Min Kim, Hoon-Taek Chung.Thefirst cycle characteristics of Li[Ni such as Jung-Min Kim
1/3Co
1/3Mn
1/3] O
2Charged up to 4.7V.Electrochimica Acta, 49 (2004): 937-944) adopt LiOHH
2O, Ni (OH)
2, Co (NO
3)
26H
2O, Mn
3O
4As raw material, with ethanol mixing and ball milling after drying; Dried powder obtains final product at 950 ℃ of insulation 12h.People (Masaki Yoshio, Hideyuki Noguchi, et al.Preparation andproperties of LiCo such as Masaki Yoshio
yMn
xNi
1-x-yO
2As a) uses γ-MnOOH as the manganese source, and Co3O
4, LiOHH
2O, Ni (OH)
2After the mixing, grind with mortar; The mixture tablet forming obtains final product at 700-900 ℃ of sintering 20h.People (Zhangxiang Wang, Yucheng Sun, et al.Electrochemicalcharacterization of positive electrode material LiNi such as Zhaoxiang Wang
1/3Co
1/3Mn
1/3O
2Andcompatibility with electrolyte for lithium-ion batteries.Journal ofElectrochemical Society, 151 (6), 2004:A914-A921) use Ni
2O
3, Co
2O
3, MnO
2To a certain degree excessive LiOHH
2O mixes back sintering 24h in 850-1100 ℃ of temperature range, also can obtain intact laminate structure.
In article of delivering and patent, do not see at present the report that adopts with same raw materials of the present invention and synthetic this material of method as yet.
Summary of the invention
The object of the present invention is to provide a kind of employing low fever solid phase reaction to prepare LiCo
1-2x-yNi
xMn
xM
yO
2The method of material has solved the synthetic LiCo of high temperature solid-state
1/3Ni
1/3Mn
1/3O
2Temperature height in the positive electrode material process, the time is long, the problem that energy consumption is high; Solve complex process in the liquid phase building-up process, multicomponent mixture is not easy by metering than sedimentary problem.
The present invention adopts the low fever solid phase reaction method, prepares presoma in two steps.The first step is respectively with lithium hydroxide (LiOH.H
2O) mixed in pulverizer 1～2 minute by stoichiometric ratio with oxalic acid (citric acid or sugar), its ratio is Li: H
2C
2O
4=1: 0.8～1.2; The acetate of cobalt nickel manganese was mixed in pulverizer 1～2 minute in proportion, mix, its ratio is Co: Ni: Mn=1: 1: 1.Second step was after two kinds of material ball millings that the first step mixes were mixed in 2～6 hours, 120～150 ℃ of vacuum-dryings, to prepare presoma.
Product preparation: the presoma for preparing was obtained final product in 6～12 hours 500～800 ℃ of roastings.
At preparation LiCo
1/3Ni
1/3Mn
1/3O
2Step in, can in the acetate of cobalt nickel manganese, add 0～0.1 mole Fe, V, acetate or the oxide compound of Cr, Al.Obtain final product LiCo
1-2x-yNi
xMn
xM
yO
2, x=0.3～0.4 wherein, y=0～0.1.
The present invention adopts low fever solid phase reaction to prepare presoma, utilizes organic acid and LiOH.H earlier
2O forms the complex compound of lithium, and then with Ni, Co, Mn salt mix the formation presoma.
What people's such as the present invention and Yang Huo patent [publication number CN1461064A low fever solid phase reaction prepares lithium manganese oxide] was different is, our preparation be excessive component material, and adopt two-step approach to prepare the homogeneity that presoma more helps product.The method invention is simple to operate, and synthesis temperature is low, can reach the performance of liquid phase synthetic materials simultaneously.
Description of drawings
Fig. 1 is low-heat synthetic LiCo of the present invention
1/3Ni
1/3Mn
1/3O
2XRD figure, Fig. 1 (a) is by embodiment 1 preparation, and Fig. 1 (b) is by embodiment 2 preparations, and Fig. 1 (c) is by embodiment 3 preparations.
Fig. 2 is high temperature solid state reaction and liquid phase coprecipitation synthetic LiCo
1/3Ni
1/3Mn
1/3O
2XRD figure.Fig. 2 (a) high temperature solid-state is synthetic, and is synthetic by the method for Comparative Examples 1; Fig. 2 (b) liquid phase coprecipitation is synthetic, and is synthetic by the method for Comparative Examples 2.
Fig. 3 is low-heat synthetic LiCo of the present invention
1/3Ni
1/3Mn
1/3O
2Charging and discharging curve figure.Fig. 3 (a) is by the preparation of embodiment 1 method, and Fig. 3 (b) is prepared by embodiment 2 methods.Charging and discharging currents density 100mA/g, charging/discharging voltage scope 4.35-2.7V.X-coordinate is specific storage (mAh/g), and ordinate zou is voltage (V).
Fig. 4 is high temperature solid state reaction and liquid phase coprecipitation synthetic LiCo
1/3Ni
1/3Mn
1/3O
2Charging and discharging curve figure.Fig. 4 (a) is prepared by Comparative Examples 1 method; Fig. 4 (b) is prepared by Comparative Examples 2 methods.Charging and discharging currents density 40mA/g, charging/discharging voltage scope 4.35-2.7V.X-coordinate is specific storage (mAh/g), and ordinate zou is voltage (V).
Fig. 5 is low-heat synthetic LiCo of the present invention
1/3Ni
1/3Mn
1/3O
2Specific storage and cycle life figure with the Comparative Examples synthetic sample.X-coordinate is a cycle index, and ordinate zou is specific storage (mAh/g).The cycle performance contrast of 4 samples.
Embodiment
Further specify method of the present invention by the following examples.
1, preparation LiCo
1/3Ni
1/3Mn
1/3O
2
Execute example 1:
1) takes by weighing oxalic acid 12.67g and LiOHH respectively
2O4.417g becomes thick by 1: 1 mixed in molar ratio.
2) with (1: 1: the 1) weighing in molar ratio of cobaltous acetate (8.344g), nickelous acetate (8.464g), manganous acetate (8.252g), join 1 after mixing) in the powder that obtains, (Co+Ni+Mn): Li=1: 1.Grind and evenly obtain pink colour pasty state presoma.
3) pink colour pasty state presoma is taken out 150 ℃ of vacuum-drying 24h.
4) presoma is put into crucible oven, be warming up to 350 ℃ of insulation 4h, continue to be warming up to 700 ℃, insulation 15h with 5 ℃/min.Cool to room temperature by 5 ℃/min, carried out 600 ℃ of temper 6 hours behind 240 mesh sieves excessively.
Embodiment 2:
1) takes by weighing citric acid 21.120g and LiOHH respectively
2O4.417g becomes thick by 1: 1 mixed in molar ratio.
2) with 2 in the example 1).
3) pink colour pasty state presoma takes out, 150 ℃ of vacuum-drying 24h.
4) presoma is put into crucible oven, be warming up to 400 ℃ of insulation 4h, continue to be warming up to 700 ℃, insulation 15h with 5 ℃/min.Cool to room temperature by 5 ℃/min, carried out 600 ℃ of temper 6 hours behind 240 mesh sieves excessively.
Execute example 3:
1)-3) go on foot with embodiment 1,
4) presoma is put into crucible oven, be warming up to 350 ℃ of insulation 4h, continue to be warming up to 600 ℃, insulation 15h with 5 ℃/min.Cool to room temperature by 5 ℃/min, carried out 600 ℃ of temper 6 hours behind 240 mesh sieves excessively.
Comparative Examples 1: high temperature solid-state is synthetic
The acetate of Ni, Co, Mn, Li is pressed the stoichiometric ratio mixing and ball milling, Ni: Co: Mn=1: 1: 1, (Ni+Co+Mn): Li=1: 1.Dried presoma is put into crucible oven, is warming up to 350 ℃ of insulation 4h with 5 ℃/min, continues to be warming up to 950 ℃, insulation 15h.Cool to room temperature by 5 ℃/min, carried out 600 ℃ of temper 6 hours behind 240 mesh sieves excessively.
Comparative Examples 2: liquid phase coprecipitation is synthetic
Raw material adopts CoSO
47H
2O, NiSO
46H
2O, MnSO
4H
2O is made into certain density solution (0.1mol/0.4L) with metal sulfate, (Ni: Co: Mn)=1: 1: 1.Aforesaid liquid slowly is added drop-wise to the LiOHH of continuous stirring
2In the O solution (0.2mol/0.4L), control metallic solution and LiOHH
2The concentration of O solution, rate of addition (2-3s/ drips) and churning time (5.5h), continuous dripping alkali liquid (LiOH) (0.4mol/0.4L) is controlled between the pH value maintenance 13-14 of reaction solution in the reaction process.
After reaction finishes,, remove SO with deionized water repetitive scrubbing throw out
4 =Ion.The suction filtration gained is deposited in 120 ℃ of dry 12h down, with stoichiometric LiOHH
2Carry out pyroprocessing after O (1: the 1) mixing and ball milling.Sintering schedule is incubated 15h for be warming up to 600 ℃ of insulation 4h down with 5 ℃/min down at 900 ℃, carries out 600 ℃ of temper 6h then.
4 kinds of materials of above-mentioned synthetic are added conductive agent (10%) respectively, and the sticking film that is pressed into of binding agent (5%) is formed test cell with metallic lithium, carries out the constant current charge-discharge experiment.The battery charging and discharging electric current is 100mA/g among the embodiment 1,2, and the charging/discharging voltage scope is controlled between the 2.7-4.35V.The battery charging and discharging electric current is 40mA/g in the Comparative Examples 1,2, and the charging/discharging voltage scope is controlled between the 2.7-4.35V.
By the XRD figure of Fig. 1 and Fig. 2 as seen, five sample diffraction peak positions are consistent with the diffraction peak of R 3m spacer, illustrate to have formed good laminate structure.
By Fig. 3, Fig. 4 as seen, adopt the LiCo of low-heat solid phase synthesis process preparation
1/3Ni
1/3Mn
1/3O
2Material has more excellent performance, and the material that still can reach the liquid-phase synthesis process preparation when the 100mA/g constant current charge-discharge is at 40mA/g constant current charge-discharge identical specific storage and cycle performance.But the low-heat solid phase synthesis process is simple, low 200 ℃ of synthesis temperature.In 4 samples, the material property of high temperature solid state reaction preparation is the poorest, and specific storage only is 140mAh/g when the 40mA/g constant current charge-discharge.And decay is very fast.
Claims (3)
1, a kind of employing low fever solid phase reaction prepares LiCo
1/3Ni
1/3Mn
1/3O
2The method of material is characterized in that:
A, presoma preparation:
Prepare presoma in two steps, the first step is respectively with lithium hydroxide LiOH.H
2O and oxalic acid H
2C
2O
4Mix by stoichiometric ratio, its ratio is Li: H
2C
2O
4=1: 0.8～1.2; The acetate of cobalt nickel manganese is mixed in proportion, and its ratio is Co: Ni: Mn=1: 1: 1; Second step was after two kinds of material ball millings that the first step mixes were mixed in 2～6 hours, 120～150 ℃ of vacuum-dryings, to prepare presoma.
(b) preparation of product obtained final product LiCo with the presoma for preparing in 6～15 hours 500～800 ℃ of roastings
1/3Ni
1/3Mn
1/3O
2
2, require described preparation method according to right 1, it is characterized in that: replace oxalic acid with citric acid or sugar.
3, require described preparation method according to right 1 or 2, it is characterized in that: at preparation LiCo
1/3Ni
1/3Mn
1/3O
2Step in, in the acetate of cobalt nickel manganese, add 0～0.1 mole Fe, V, Cr, Al, acetate or the oxide compound of Li, obtain final product LiCo
1-2x-yNi
xMn
xM
yO
2, wherein, x=0.3～0.4, y=0～0.1.
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|---|---|---|---|
| CNB2005100116761A CN1269242C (en) | 2005-04-30 | 2005-04-30 | Method for preparing laminar oxide material of lithium, cobalt, nickel and manganese through solid phase reaction in low heat |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100116761A CN1269242C (en) | 2005-04-30 | 2005-04-30 | Method for preparing laminar oxide material of lithium, cobalt, nickel and manganese through solid phase reaction in low heat |
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|---|---|
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| CN1269242C CN1269242C (en) | 2006-08-09 |
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Cited By (4)
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| CN1330602C (en) * | 2006-02-28 | 2007-08-08 | 济宁市无界科技有限公司 | Lithium ion cell blended positive pole material and its preparing method |
| CN102163709A (en) * | 2011-03-09 | 2011-08-24 | 合肥工业大学 | Cobalt nickel manganese lithium oxide-cooper oxide compound positive material for lithium ion battery and preparation method thereof |
| CN101677125B (en) * | 2008-09-16 | 2013-07-10 | 中国科学院福建物质结构研究所 | Method for preparing layered cathode material of lithium ion battery |
| CN104362329A (en) * | 2014-09-18 | 2015-02-18 | 长沙矿冶研究院有限责任公司 | Method for preparing lithium-rich manganese-based layered lithium battery cathode material based on efficient solid-phase chemical complexation reaction |
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| CN102064317B (en) * | 2009-11-13 | 2014-11-19 | 深圳市比克电池有限公司 | LiFe1-xMxPO4 compound containing carbon element and preparation method thereof |
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2005
- 2005-04-30 CN CNB2005100116761A patent/CN1269242C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1330602C (en) * | 2006-02-28 | 2007-08-08 | 济宁市无界科技有限公司 | Lithium ion cell blended positive pole material and its preparing method |
| CN101677125B (en) * | 2008-09-16 | 2013-07-10 | 中国科学院福建物质结构研究所 | Method for preparing layered cathode material of lithium ion battery |
| CN102163709A (en) * | 2011-03-09 | 2011-08-24 | 合肥工业大学 | Cobalt nickel manganese lithium oxide-cooper oxide compound positive material for lithium ion battery and preparation method thereof |
| CN102163709B (en) * | 2011-03-09 | 2013-01-09 | 合肥工业大学 | Cobalt nickel manganese lithium oxide-cooper oxide compound positive material for lithium ion battery and preparation method thereof |
| CN104362329A (en) * | 2014-09-18 | 2015-02-18 | 长沙矿冶研究院有限责任公司 | Method for preparing lithium-rich manganese-based layered lithium battery cathode material based on efficient solid-phase chemical complexation reaction |
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| Publication number | Publication date |
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| CN1269242C (en) | 2006-08-09 |
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