CN1321881C - Method for preparing Li, Ni, Mn oxide material by adopting low-heat solid phase reaction - Google Patents
Method for preparing Li, Ni, Mn oxide material by adopting low-heat solid phase reaction Download PDFInfo
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- CN1321881C CN1321881C CNB2005100865055A CN200510086505A CN1321881C CN 1321881 C CN1321881 C CN 1321881C CN B2005100865055 A CNB2005100865055 A CN B2005100865055A CN 200510086505 A CN200510086505 A CN 200510086505A CN 1321881 C CN1321881 C CN 1321881C
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 16
- 238000003746 solid phase reaction Methods 0.000 title claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 title claims description 8
- 229910052744 lithium Inorganic materials 0.000 title description 9
- 229910052748 manganese Inorganic materials 0.000 title description 6
- 239000011572 manganese Substances 0.000 claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims abstract description 4
- 239000012467 final product Substances 0.000 claims abstract description 4
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 4
- 206010037660 Pyrexia Diseases 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 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 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 229940071125 manganese acetate Drugs 0.000 abstract 1
- 229940078494 nickel acetate Drugs 0.000 abstract 1
- 238000007600 charging Methods 0.000 description 20
- 238000007599 discharging Methods 0.000 description 20
- 229910013716 LiNi Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010532 solid phase synthesis reaction Methods 0.000 description 7
- 229910052596 spinel Inorganic materials 0.000 description 7
- 239000011029 spinel Substances 0.000 description 7
- 238000009413 insulation Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 3
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000003836 solid-state method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000002910 structure generation Methods 0.000 description 1
- 239000000126 substance Substances 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
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a method for preparing LiNi0.5Mn1.5O4 materials by adopting a low heat solid-phase reaction, which belongs to the technical field of the anode material preparation of a lithium ion battery. A precursor is prepared by two steps; in the first step, lithium hydroxide LiOH. H2O and oxalic acid H2C2O4 are mixed according to a stoichiometric ratio, and the ratio of Li to H2C2O4 is equal to 1: 0.8 to 1.2; nickel acetate and manganese acetate are proportionally and uniformly mixed, and the ratio of Ni to Mn is equal to 0.9 to 1.1: 3; in the second step, after ball milling for 1.5 to 2.5 hours, two kinds of materials well mixed in the first step are mixed and dried in vacuum at a temperature of 120 to 150 DEG C to obtain a precursor. The well prepared precursor is calcined at a temperature of 500 to 800 DEG C for 6 to 15 hours to obtain the final product LiNi0.5Mn1.5O4. The present invention has the advantages that the polycomponent raw material is prepared, the precursor is prepared by a two-step method, which is beneficial to the product homogeneity, the operation is simple, and the synthesis temperature is low.
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 LiM
xNi
0.5-xMn
1.5O
4The method of material, M is a metal, is used as anode material for lithium-ion batteries.
Technical background
Lithium ion battery is owing to its height ratio capacity is subjected to liking of users, also being subjected to numerous investigators' attention. the lithium manganese oxide of spinel type becomes the focus of current anode material for lithium-ion batteries research because of advantage such as inexpensive, practical, environmentally safe, high-energy-density, be considered to substitute one of the most competitive candidate material of the sour lithium of stratiform cobalt, lithium nickelate.By cube changing cubic phase mutually into, in this phase transition process, the unitary volume of structure cell has increased by 6.5% to the lithium manganese oxide of spinel type, causes spinel structure generation deformation in the deep discharge process, produces destruction, makes capacity attenuation.So it can only discharge and recharge in the 4V zone, but tangible power loss is arranged.In order to improve the cycle performance in 4V zone, people have adopted the doping transition element in the structure of spinel, discovery bigger voltage platform occurred after being doped in the spinel near the 5V, the capacity of battery and voltage platform depend on the type and the concentration of transition metal.The benefit of 5V battery is to obtain high power density.Certainly so high voltage is had higher requirement with regard to the structure and the chemical stability of counter electrode material and electrolytic solution.Breakthrough in electrolytic solution research makes research 5V battery become possibility.The investigator of various countries is for adopting the different transition element that mixes to prepare LiM with the Mn that different dopings substitutes in the spinel
xMn
2-xO
4(M=Li, Co, Mg, Cr, Ni, Fe, Ti Zn) studies.The adulterated 5V positive electrode material of Ni LiM in various materials
xNi
0.5-xMn
1.5O
4, because of its have the higher voltage platform and preferably the capacity cycle performance to have caused scholars' research interest.
Present LiM
xNi
0.5-xMn
1.5O
4The synthetic method of material adopts high temperature solid-state method and sol-gel method to synthesize substantially.For example, people (Yasushi Idemoto, Hirosuke Narai, Nobuyubi Koura, Journal of Power Sources, 119-121 (2003) 125-129) such as Yasushi Idemoto adopts the Li of high temperature solid-state method with stoichiometric ratio
2CO
3, MnO
2And Ni (OH)
2Mix, in 600 ℃ air, carry out pre-burning 24h, then at 700 ℃ O
2Sintering is 24 hours in the stream, at last through the sample of temper system under 500 ℃ the oxygen atmosphere.People such as KohTakahashi (Koh Takahashi, Motoharu Saitoh, Mitsuru Sano, Miho Fujita, Journalof The Electrochemical Society, 151 (1) A173-A177 (2004)) also adopt sol-gel method with 0.1mol LiNO
3, 0.15mol Mn (NO
3)
26H
2O and 0.05mol Ni (NO
3)
26H
2O is dissolved in the 20ml deionized water and is made into the aqueous solution, and the PVA that adds different amounts then forms colloidal sol, impels mixture to react under 150 ℃.The black powder of last gained uses the conventional electrical stove respectively 650,700 through ball milling, the samples of 5 hours systems of 750 ℃ of following sintering.People (Kingo Ariyoshi such as Kingo Ariyoshi, Yasunobu Iwakoshi, NoriakiNakayama, and Tsutomu Ohzuku, Joumal of The Electrochemical Society, 151 (2) A296-A303 (2004)) with the oxyhydroxide and the Li (OH) of nickel and manganese
2At 1000 ℃ of following sintering 12h, handled 48 hours down at 700 ℃ then, promptly get required product through grinding.
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 LiM
xNi
0.5-xMn
1.5O
4The method of material has solved the synthetic LiM of high temperature solid-state
xNi
0.5-xMn
1.5O
4Temperature height in the positive electrode material process, the time is long, the problem that energy consumption is high; Solve complex process in the collosol and gel 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 (LiOHH
2O) mixed in micromill 1 minute by stoichiometric ratio with oxalic acid (hexanodioic acid, citric acid or sugar), its ratio is Li: H
2C
2O
4=1: 0.8～1.2; The acetate of nickel manganese was mixed 1 minute in micromill in proportion, mix, its ratio is Ni: Mn=0.9～1.1: 3.Second step was two kinds of material ball millings that the first step is mixed after 1.5～2.5 hours, 120～150 ℃ of vacuum-dryings, prepared presoma.
Product preparation: the presoma for preparing was obtained final product LiNi in 6～15 hours 500～800 ℃ of roastings
0.5Mn
1.5O
4
At preparation LiNi
0.5Mn
1.5O
4Step in, can in the acetate of nickel manganese, add Co, Fe, V, the Cr of stoichiometric ratio, acetate or the oxide compound of Al.Obtain final product LiM
xNi
0.5-xMn
1.5O
4, x=0～0.1 wherein.
The present invention adopts low fever solid phase reaction to prepare presoma, utilizes organic acid and LiOHH earlier
2O forms the complex compound of lithium, and then with Ni, Mn salt mixes 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 that 5V is (with respect to Li
+/ Li) Li, Ni, Mn oxide material, and people's such as Yang Huo invention is that 3V and 4V are (with respect to Li
+/ Li) Li, Ni, Mn oxide material; We adopt two-step approach to prepare the homogeneity that presoma more helps product.The present 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 the LiNi of low-heat solid phase synthesis of the present invention
0.5Mn
1.5O
4XRD figure is by embodiment 1 preparation.
Fig. 2 is the LiNi of low-heat solid phase synthesis of the present invention
0.5Mn
1.5O
4XRD figure is by embodiment 2 preparations.
Fig. 3 is the LiNi of low-heat solid phase synthesis of the present invention
0.5Mn
1.5O
4XRD figure is by embodiment 3 preparations.
Fig. 4 is the LiNi of low-heat solid phase synthesis of the present invention
0.5Mn
1.5O
4Charging and discharging curve figure.Prepare by embodiment 1 method.Charging and discharging currents density 20mA/g, charging/discharging voltage scope 4.95-3.5V.X-coordinate is specific storage (mAh/g), and ordinate zou is voltage (V).
Fig. 5 is the LiNi of low-heat solid phase synthesis of the present invention
0.5Mn
1.5O
4Charging and discharging curve figure.Prepare by embodiment 2 methods.Charging and discharging currents density 20mA/g, charging/discharging voltage scope 4.95-3.5V.X-coordinate is specific storage (mAh/g), and ordinate zou is voltage (V).
Fig. 6 is the LiNi of low-heat solid phase synthesis of the present invention
0.5Mn
1.5O
4Charging and discharging curve figure.Prepare by embodiment 3 methods.Charging and discharging currents density 20mA/g, charging/discharging voltage scope 4.95-3.5V.X-coordinate is specific storage (mAh/g), and ordinate zou is voltage (V).
Fig. 7 is the prepared LiNi of Comparative Examples 1-3 (citing document)
0.5Mn
1.5O
4Sample charging and discharging curve figure.Prepare by Comparative Examples 1 method.Charging and discharging currents density 0.2mA/cm
2, charging/discharging voltage scope 5.0-3.5V.X-coordinate is specific storage (mAh/g), and ordinate zou is voltage (V).
Fig. 8 is the prepared LiNi of Comparative Examples 1-3 (citing document)
0.5Mn
1.5O
4Sample charging and discharging curve figure.By the preparation of Comparative Examples 2 methods, charging and discharging currents density 0.2mA/cm
2, charging/discharging voltage scope 5.0-3.5V.X-coordinate is specific storage (mAh/g), and ordinate zou is voltage (V).
Fig. 9 is the prepared LiNi of Comparative Examples 1-3 (citing document)
0.5Mn
1.5O
4Sample charging and discharging curve figure.By the preparation of Comparative Examples 3 methods, charging and discharging currents density 0.2mA/cm
2, charging/discharging voltage scope 5.0-3.5V.X-coordinate is specific storage (mAh/g), and ordinate zou is voltage (V).
Embodiment
Further specify method of the present invention by the following examples.
1, preparation LiNi
0.5Mn
1.5O
4
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: the 3) weighing in molar ratio of nickelous acetate (12.696g), manganous acetate (37.135g), join 1 after mixing) in the powder that obtains, (Ni+Mn): Li=2: 1.Grind and evenly obtain light green 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 500 ℃, insulation 15h with 5 ℃/min.Cool to room temperature by 5 ℃/min, carried out 350 ℃ of temper 6 hours behind 240 mesh sieves excessively.
Execute example 2:
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 350 ℃ 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 700 ℃, insulation 15h with 5 ℃/min.Cool to room temperature by 5 ℃/min, carried out 350 ℃ of temper 6 hours behind 240 mesh sieves excessively.
3 kinds of materials of above-mentioned synthetic are added acetylene black (conductive agent 10%) respectively, and tetrafluoroethylene (binding agent 5%) backing film forming as positive pole, is formed test cell with metallic lithium, carries out the constant current charge-discharge experiment.The battery charging and discharging electric current is 20mA/g, and the charging/discharging voltage scope is controlled between the 3.5-4.95V.
Comparative Examples l: high temperature solid-state is synthesized (being selected from Yasushi Idemoto, Hirosuke Narai, NobuyubiKoura, Journal of Power Sources, 119-121 (2003) 125-129)
Li with stoichiometric ratio
2CO
3, MnO
2And Ni (OH)
2Mix, in 600 ℃ air, carry out pre-burning 24h, then 700 ℃ 0
2Sintering is 24 hours in the stream,
Comparative Examples 2: high temperature solid-state increases thermal treatment (being selected from Yasushi Idemoto, HirosukeNarai, Nobuyubi Koura, Journal of Power Sources, 119-121 (2003) 125-129) under the oxidizing atmosphere
The system of getting among the Comparative Examples l is each got sample and is in the end carried out temper through (pressure is 2.02MPa) under 500 ℃ the oxygen atmosphere.
Comparative Examples 3. sol-gel methodes (being selected from Yasushi Idemoto, Hirosuke Narai, Nobuyubi Koura, Joumal of Power Sources, 119-12l (2003) 125-129)
With LiN0
3, Mn (N0
3)
26H
20 and Ni (N0
3)
26H
20 adds PVA forms colloidal sol, impels mixture to react under 150 ℃.The powder of last gained is incubated 24 hours under 500 ℃ of oxygen atmospheres, and then sintering was prepared from 24 hours under 700 ℃ of oxygen atmospheres.
By the XRD figure of Fig. 1 as seen, three sample diffraction peak positions and Fd
The diffraction peak unanimity of m spacer illustrates to have formed good spinel structure.
By Fig. 2, adopt the LiNi of low-heat solid phase synthesis process preparation
0.5Mn
L.50
4Material has good performance.
Claims (1)
1, a kind of employing low fever solid phase reaction prepares LiM
xNi
0.5-xMn
1.5O
4Method, wherein, x=0～0.1 is characterized in that: concrete processing step is:
A, presoma preparation: prepare presoma in two steps, the first step is respectively with lithium hydroxide LiOHH
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 nickel manganese is mixed in proportion, and its ratio is Ni: Mn=0.9～1.1: 3; Second step was two kinds of material ball millings that the first step is mixed after 1.5～2.5 hours, 120～150 ℃ of vacuum-dryings, prepared presoma; In the acetate of nickel and manganese, add 0～0.1 mole Fe, V, Cr, Al, acetate or the oxide compound of Co;
The preparation of b, product: the presoma for preparing was obtained final product in 6～15 hours 500～800 ℃ of roastings.
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|---|---|---|---|
| CNB2005100865055A CN1321881C (en) | 2005-09-23 | 2005-09-23 | Method for preparing Li, Ni, Mn oxide material by adopting low-heat solid phase reaction |
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|---|---|---|---|
| CNB2005100865055A CN1321881C (en) | 2005-09-23 | 2005-09-23 | Method for preparing Li, Ni, Mn oxide material by adopting low-heat solid phase reaction |
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| Publication Number | Publication Date |
|---|---|
| CN1765732A CN1765732A (en) | 2006-05-03 |
| CN1321881C true CN1321881C (en) | 2007-06-20 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102064317A (en) * | 2009-11-13 | 2011-05-18 | 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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| CN102263258A (en) * | 2010-08-10 | 2011-11-30 | 中信国安盟固利动力科技有限公司 | Positive electrode material of high voltage lithium battery |
| CN103443993A (en) | 2011-03-24 | 2013-12-11 | 日本电气株式会社 | Secondary battery |
| CN109713277B (en) * | 2018-12-29 | 2022-04-19 | 蜂巢能源科技股份有限公司 | Lithium ion battery positive electrode material, preparation method and lithium ion battery |
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