CN102394296A - Anode material for lithium battery and preparation method thereof, and lithium battery anode and lithium battery - Google Patents
Anode material for lithium battery and preparation method thereof, and lithium battery anode and lithium battery Download PDFInfo
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Abstract
The invention provides an anode material for lithium battery, and the anode material is expressed by a general formula LiNi0.5-xAl2xMn1.5-xO4, wherein x satisfies a relation of: 0<2x<=0.5. The invention also provides a preparation method of the anode material and a lithium battery anode and a lithium battery that are prepared from the anode material. The anode material provided by the invention has low cost, good environment friendliness, high purity, good high temperature and heavy current cycle characteristic.
Description
Technical field
The present invention relates to field of batteries, particularly a kind of positive electrode that is used for lithium battery and preparation method thereof, lithium battery anode and lithium battery.
Background technology
Current, the mankind are being faced with the double challenge that resource is estimated and living environment worsens.For this reason, new material is being made great efforts to research and develop in countries in the world, advances the new concept of low-carbon (LC) life, promotes human society to turn to sustainable development mode energy-saving, capable of circulation by present high energy consumption, the high flow rate life mode of production.Be specially the application of wideling popularize clean energy resource,, and use hybrid vehicle or pure electric automobile to replace using at present the orthodox car of gasoline like the application of solar energy, wind energy at power field.
The application of clean energy resource and novel vapour all be unable to do without medium-and-large-sized energy-storage battery and electrokinetic cell.In numerous energy-storage batteries and electrokinetic cell; Lithium rechargeable battery is owing to have high energy density and long useful life; Replaced traditional ni-mh/NI-G secondary cell gradually, it has the great development prospect at emerging fields such as new-energy automobile, wind-powered electricity generation energy storage and solar energy storages.
Lithium rechargeable battery comprises positive pole, negative pole, is arranged on barrier film and electrolyte between positive pole and the negative pole.Wherein, positive pole comprises matrix and is coated in the coating material on this matrix that coating material comprises positive electrode (positive active material), electric conducting material and binding agent.Wherein, positive electrode is the crucial raw material of lithium rechargeable battery, because positive electrode occupies bigger weight ratio in lithium rechargeable battery, so the positive electrode performance has determined build, fail safe and the electric property of battery.
The positive electrode that uses in the current lithium battery is LiCoO mostly
2, also have partial L iFePO
4, LiMn
2O
4And LiNi
1-xCo
xO
2
Cobalt acid lithium has higher specific capacity and cycle characteristics preferably.But, because the abundance of cobalt element in the earth's crust is low, belong to rare metal, therefore cost an arm and a leg, also cause the cost of this kind material higher thus.In addition, cobalt element also has certain toxicity, and is after being discarded by the battery of cobalt acid lithium preparation, bigger to the harm of environment.Therefore, the comparatively cheap and environmental-protecting performance of a kind of price positive electrode preferably need be provided.
LiFePO
4Have Stability Analysis of Structures, raw material is cheap, and cyclicity and fail safe are better, to advantages such as environmental pressure are less, but problem such as it is higher also to exist synthetic cost, and energy density is lower.
Spinel lithium manganate LiMn
2O
4Have that fail safe is good, multiplying power property is good, price is low, advantages such as environmental protection also be present a kind of main flow positive electrode, but its energy density are on the low side, and cycle performance and high-temperature behavior are relatively poor, are difficult to satisfy the requirement of large-sized power lithium ion battery and energy-storage battery.
LiNi
0.5Mn
1.5O
4Have the same crystal structure of LiMn2O4, therefore also have advantage safe, that multiplying power property is good.Its operating voltage of what is more important is 4.7V, is higher than LiMn
2O
4, therefore have higher power density.But some shortcomings are also arranged, and such as being difficult to prepare the high-purity sample, high temperature and big current cycle characteristic such as need improve at problem.
In view of based on above-mentioned some, the present invention considers to have selected in positive electrode, to use aluminium element, prepares thus that cost is lower, the feature of environmental protection is better, purity is high and has good high-temperature and the positive electrode of big current cycle characteristic.
Summary of the invention
Deficiency to prior art; The technical problem that the present invention solves is to provide a kind of positive electrode that is used for lithium battery and preparation method thereof, and the positive electrode cost of preparation provided by the invention is lower, the feature of environmental protection is better, purity is high and have good high-temperature and big current cycle characteristic.
For solving the problems of the technologies described above, technical scheme of the present invention is achieved in that a kind of positive electrode that is used for lithium battery, and especially, said positive electrode is by general formula LiNi
0.5-xAl
2xMn
1.5-xO
4Expression, in this general formula, 0＜2x≤0.5.
Preferably, in above-mentioned positive electrode, in the said general formula, 0.1≤2x≤0.2.
Preferably, in above-mentioned positive electrode, in the said general formula, 2x value 0.1 or 0.15.
Correspondingly, the present invention also provides a kind of preparation method of above-mentioned positive electrode, comprises the steps:
A), adopt the liquid-phase mixing method, manganese source compound, nickel source compound and aluminum source compound are mixed in proportion, obtain mixed solution;
B), said mixed solution is carried out spray drying treatment, obtain first mixture;
C), said first mixture is heat-treated, obtain nickel aluminium Mn oxide precursor;
D), said nickel aluminium Mn oxide precursor and Li source compound are mixed and grind, obtain second mixture;
E), said second mixture is heat-treated, obtain positive electrode.
Preferably, in the preparation method of above-mentioned positive electrode, the mol ratio of nickel, aluminium and manganese is 0.4～0.475: 0.05～0.2 in the said step a): 1.4～1.475.
Preferably, in the preparation method of above-mentioned positive electrode, the mol ratio of nickel aluminium Mn oxide precursor and Li source compound is 0.9～1: 1～1.1 in the said step d).
Preferably, in the preparation method of above-mentioned positive electrode, heat treated temperature is 700～1000 ℃ in the said step c).
Preferably, in the preparation method of above-mentioned positive electrode, heat treatment period is 10～48h in the said step c).
Preferably, in the preparation method of above-mentioned positive electrode, heat treated temperature is 500～800 ℃ in the said step e).
Preferably, in the preparation method of above-mentioned positive electrode, heat treatment period is 10～48h in the said step e).
Preferably, in the preparation method of above-mentioned positive electrode, said manganese source compound is a manganese acetate, and said nickel source compound is a nickel acetate, and said aluminum source compound is an aluminum nitrate, and said Li source compound is a lithium hydroxide.
The present invention also provides a kind of lithium battery anode, comprises matrix and the coating material that places matrix surface, and said coating material comprises above-mentioned described positive electrode, electric conducting material and binding agent.
The present invention also provides a kind of lithium battery, comprising: above-mentioned described lithium battery anode, negative pole, be arranged on barrier film and electrolyte between positive pole and the negative pole
The positive electrode that utilizes preparation method of the present invention to obtain possesses higher purity and good high-temperature and big current cycle characteristic, and simultaneously, owing to adopted aluminium element, cost is lower, good environmental protection.
Description of drawings
In order to be illustrated more clearly in the technical scheme in the embodiment of the invention; The accompanying drawing of required use is done to introduce simply in will describing embodiment below; Obviously, the accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills; Under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is preparation method's flow chart of positive electrode in the specific embodiment of the invention;
Fig. 2 is the XRD figure spectrum of the embodiment of the invention 1～3 and the positive electrode of comparative example 1 acquisition;
Fig. 3 is the made cycle characteristics curve of Experimental cell under the little electric current of room temperature of positive electrode by embodiment 1～3 and comparative example 1 preparation;
Fig. 4 is the made cycle characteristics curve of Experimental cell under the big electric current of high temperature of positive electrode by embodiment 1～3 and comparative example 1 preparation.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of positive electrode that is used for lithium battery, have general formula LiNi
0.5-xAl
2xMn
1.5-xO
4Structure, 0＜2x in the general formula≤0.5.Preferably, 0.1≤2x≤0.2.Preferred, the 2x value is 0.1 or 0.15.
This positive electrode comprises lithium primary battery and lithium rechargeable battery in order to the preparation energy storage device.
This positive electrode has spinel structure and 4.7 couchers are made voltage platform.
Positive electrode provided by the invention is a raw material with the comparatively cheap manganese of price, lithium, nickel and aluminium, so cost is lower.
Positive electrode provided by the invention adopts aluminium element, does not have toxicity, can not produce harmful effect to environment after discarding, so good environmental protection.
Positive electrode provided by the invention adopts aluminium element, can improve the diffusion velocity of lithium ion in crystal, thereby can improve the high temperature and big current cycle characteristic of above-mentioned positive electrode.
The present invention also provides a kind of preparation method of above-mentioned positive electrode, comprises the steps:
A), adopt the liquid-phase mixing method, manganese source compound, nickel source compound and aluminum source compound are mixed in proportion, obtain mixed solution;
B), said mixed solution is carried out spray drying treatment, obtain first mixture;
C), said first mixture is heat-treated, obtain nickel aluminium Mn oxide precursor;
D), said nickel aluminium Mn oxide precursor and Li source compound are mixed and grind, obtain second mixture;
E), said second mixture is heat-treated, obtain positive electrode.
Among the above-mentioned preparation method provided by the invention, step a), step b) and step c) are the operations of preparation nickel aluminium Mn oxide precursor.For each raw material is fully mixed, the present invention at first adopts the liquid-phase mixing method, manganese source compound, nickel source compound and aluminum source compound is mixed in proportion, thereby each element is mixed on molecular level, has guaranteed the high-purity of product.
For the mode of liquid-phase mixing, the present invention preferably is solvent with the deionized water, is raw material with water-soluble aluminum source compound, water-soluble nickel source compound and water-soluble manganese source compound, and above-mentioned raw materials is soluble in water, obtains mixed solution.Preferably, in the above-mentioned raw materials, the mol ratio of nickel, aluminium and manganese is 0.4～0.475: 0.05～0.2: 1.4～1.475.
Li source compound preferably adopts lithium acetate, lithium nitrate, lithium hydroxide or lithium carbonate; Water-soluble nickel source compound preferably adopts nickel acetate, nickel nitrate, nickel chloride or nickelous sulfate; Water-soluble manganese source compound preferably adopts manganese acetate, manganese nitrate, manganese chloride or manganese sulfate, and the water-soluble aluminum source compound preferably adopts aluminum nitrate.
Obtain containing the mixed solution of nickel aluminium Mn oxide precursor after the liquid-phase mixing, adopt spray drying that mixed solution is handled and just obtain precursor powder (first mixture).
Spray drying is the dry method of liquid material that in the hothouse thermal current, makes atomisation.The powder that mixed solution is carried out obtaining after the spray drying treatment has higher degree, with respect to traditional solution crystal process, spray drying process need not again to product wash, reprocessing such as drying, the operating process of simplification.And the dry run of spraying drying method is very fast, is suitable for industry and quantizes to produce.The present invention can adopt air-blast atomization seasoning, pressure type atomization drying method or rotation type atomization seasoning, and the present invention does not have special restriction to this.
The precursor powder that makes is according to the method described above heat-treated, and obtains nickel aluminium Mn oxide precursor.Heat treated temperature is preferably 700～1000 ℃, and heat treatment time is preferably 10～48 hours.More preferably, heat treated temperature is 900 ℃, and heat treatment time is preferably 20 hours.
The nickel aluminium Mn oxide precursor that obtains with the Li source compound mixing and grind, is obtained second mixture, then this second mixture is heat-treated, obtain positive electrode.In this step, the mol ratio of nickel aluminium Mn oxide precursor and Li source compound is 0.9～1: 1～1.1, and preferred mol ratio is 1: 1.In this step, heat treated temperature is preferably 500～800 ℃, and heat treatment time is preferably, 10～48 hours.More preferably, heat treated temperature is 700 ℃, and heat treatment time is preferably 24 hours.
The present invention also provides a kind of lithium battery anode, comprises matrix and the coating material that places matrix surface, and wherein coating material comprises: above-mentioned positive electrode, electric conducting material and bonding agent.
Matrix can adopt material well known to those skilled in the art in the above-mentioned positive pole, like aluminium foil.Electric conducting material is preferably conductive black super P in the coating material, and bonding agent can be polytetrafluoroethylene, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate or butadiene-styrene rubber.
Anode provided by the invention can adopt following method preparation:
Process positive plate on the matrix with being dissolved in N-methyl pyrrolidone (NMP) and being pressed in after above-mentioned positive electrode, electric conducting material, the binding agent mixing.
Accordingly, the present invention also provides a kind of lithium battery, and it comprises above-mentioned positive pole, negative pole, is arranged on barrier film and electrolyte between positive pole and the negative pole.
Positive pole provided by the invention and lithium battery preferably adopt above-mentioned positive electrode, because the raw material of above-mentioned positive electrode is comparatively cheap and difficult environment are polluted, and therefore the lithium battery by its preparation has the lower cost and the higher feature of environmental protection.
In order further to understand the present invention, positive electrode provided by the invention and preparation method thereof is described below in conjunction with Fig. 1 and embodiment.Protection scope of the present invention is not limited by the following examples.
Embodiment 1
1, with Ni: the mol ratio of Al: Mn is 0.475: 0.05: 1.475 weighing nickel acetate, and aluminum nitrate and manganese acetate mix the back and add the mixed solution that deionized water is made into 0.5mol/L;
2, mixed solution in the step 1 is obtained first mixture with the spray dryer drying;
3, with first mixture in the step 2 in air atmosphere with 900 ℃ of calcining at constant temperature 20h, behind the natural cooling, obtain nickel aluminium Mn oxide precursor Ni
0.475Al
0.05Mn
1.475O
4
4, be to mix at 1: 1 in molar ratio with nickel aluminium Mn oxide precursor in the step 3 and lithium hydroxide, grind, obtain second mixture;
5, with second mixture in the step 4 in air atmosphere with 700 ℃ of constant temperature sintering 24h, obtaining general formula is LiNi
0.475Al
0.05Mn
1.475O
4Positive electrode.
1, with Ni: the mol ratio of Al: Mn is 0.45: 0.1: 1.45 weighing nickel acetate, and aluminum nitrate and manganese acetate mix the back and add the mixed solution that deionized water is made into 0.5mol/L;
2, the mixed solution in the step 1 is obtained first mixture with the spray dryer drying;
3, with first mixture in the step 2 in air atmosphere with 900 ℃ of calcining at constant temperature 20h, behind the natural cooling, obtain nickel aluminium Mn oxide precursor Ni
0.45Al
0.1Mn
1.45O
4
4, be to mix at 1: 1 in molar ratio with nickel aluminium Mn oxide precursor in the step 3 and lithium hydroxide, grind, obtain second mixture;
5, with second mixture in the step 4 in air atmosphere with 700 ℃ of constant temperature sintering 24h, obtaining general formula is LiNi
0.45Al
0.1Mn
1.45O
4Positive electrode.
Embodiment 3
1, with Ni: the mol ratio of Al: Mn is 0.425: 0.15: 1.425 weighing nickel acetate, and aluminum nitrate and manganese acetate mix the back and add the mixed solution that deionized water is made into 0.5mol/L;
2, mixed solution in the step 1 is obtained first mixture with the spray dryer drying;
3, with first mixture in the step 2 in air atmosphere with 900 ℃ of calcining at constant temperature 20h, behind the natural cooling, obtain nickel aluminium Mn oxide precursor Ni
0.425Al
0.15Mn
1.425O
4
4, be to mix at 1: 1 in molar ratio with nickel aluminium Mn oxide precursor in the step 3 and lithium hydroxide, grind, obtain second mixture;
5, with second mixture in the step 4 in air atmosphere with 700 ℃ of constant temperature sintering 24h, obtaining general formula is LiNi
0.425Al
0.15Mn
1.425O
4Positive electrode.
Can know by Fig. 2, in embodiment 1-3,, in their X ray diffracting spectrum, all not see the existence of impurity peaks, show very high purity according to the positive electrode that preparation method of the present invention obtained.
Use the positive electrode of embodiment 1～3 preparation respectively, process positive plate according to following method, and utilize this positive plate to process CR2016 type button Experimental cell:
1, with positive electrode and conductive black super P and binding agent PVDF by 8: 1: 1 mixed, be dissolved in the N-methyl pyrrolidone (NMP), the back oven dry that stirs, pulverize, be pressed in aluminium and process positive plate on the net;
2, the positive plate that step 1 is made descends dry 5h at 130 ℃ in vacuum drying oven; Negative pole, polypropylene diaphragm and the electrolyte of dried positive plate, metal lithium sheet preparation are assembled in being full of the glove box of high-purity argon gas, obtained CR2016 type button Experimental cell.
Wherein, in the step 2 in the electrolyte supporting electrolyte be LiPF
6, solvent is an ethylene carbonate (EC) with diethyl carbonate (DEC) is to mix at 1: 1 by volume, the concentration of electrolyte is 1mol/L.
Comparative example
One, the preparation method of positive electrode:
1, with Ni: the mol ratio of Mn is 0.5: 1.5 weighing nickel acetate and manganese acetate, mixes the back and adds the mixed solution that deionized water is made into 0.5mol/L;
2, the mixed solution in the step 1 is obtained first mixture with the spray dryer drying;
3, with first mixture in the step 2 in air atmosphere with 900 ℃ of calcining at constant temperature 20h, behind the natural cooling, obtain Ni, Mn oxide precursor Ni
0.5Mn
1.5O
4
4, be to mix at 1: 1 in molar ratio with Ni, Mn oxide precursor in the step 3 and lithium hydroxide, grind, obtain second mixture;
5, with second mixture in the step 4 in air atmosphere with 700 ℃ of constant temperature sintering 24h, obtaining general formula is LiNi
0.5Mn
1.5O
4Positive electrode.
Two, by above-mentioned positive electrode LiNi
0.5Mn
1.5O
4The method for preparing battery:
1, with the positive electrode LiNi of above-mentioned preparation
0.5Mn
1.5O
4Press 8: 1: 1 mixed with conductive black super P, binding agent PVDF, be dissolved in the N-methyl pyrrolidone (NMP), stir back oven dry, pulverizing are pressed in aluminium and process positive plate on the net;
2, the positive plate that makes in the step 1 is descended dry 5h at 130 ℃ in vacuum drying oven; With dried positive plate, in being full of the glove box of high-purity argon gas, assemble, obtain CR2016 type button Experimental cell with negative pole, polypropylene diaphragm and the electrolyte of metal lithium sheet preparation.
Wherein, in the step 2 in the electrolyte supporting electrolyte be LiPF
6, solvent is an ethylene carbonate (EC) with diethyl carbonate (DEC) is to mix at 1: 1 by volume, the concentration of electrolyte is 1mol/L.
Test case 1
Carry out charge-discharge test to processing CR2016 type button Experimental cell by the positive electrode of embodiment 1～embodiment 3 and comparative example preparation, wherein, charging and discharging currents is 20 milliamperes of every grams (0.1C), and the charging/discharging voltage interval is at 3～4.9V, and probe temperature is a room temperature.
Join shown in Figure 3ly, although show comparatively stable cycle characteristics by the prepared Experimental cell of comparative example, its capacity attenuation still is apparent in view.After 50 circulations, its specific capacity drops to the every gram of less than 120 Milliampere Hours from the initial every gram of 130 Milliampere Hours, and capability retention is about 91%.And by the positive electrode made Experimental cell of enforcement 2 with embodiment 3 preparations; They are after circulating through 50 times; Its specific capacity is respectively the every gram of 121 and 120 Milliampere Hours, and capability retention is respectively 99.1% and 98.4%, improves significantly than the battery in the comparative example.By the made Experimental cell of positive electrode of embodiment 1 preparation, after through 50 circulations, its effect also has corresponding improvement than the battery in the comparative example.
The positive electrode of embodiment 1～embodiment 3 and comparative example preparation is processed CR2016 type button Experimental cell carry out charge-discharge test; Wherein, Charging current is 20 milliamperes of every grams (0.1C); Discharging current is 600 milliamperes of every grams (3C), and the charging/discharging voltage interval is at 3～4.9V, and probe temperature is 50 ℃.
Join shown in Figure 4ly, the Experimental cell that obtains through comparative example can not show comparatively stable cycle characteristics under the big electric current of high temperature, and its capacity attenuation still is apparent in view.After 50 circulations, its specific capacity drops to the every gram of less than 60 Milliampere Hours from the initial every gram of 120 Milliampere Hours, and capability retention is about 50%.And by the positive electrode made Experimental cell of embodiment 2 with embodiment 3 preparations; They are after circulating through 50 times; Its specific capacity is respectively the every gram of 114 and 104 Milliampere Hours, and capability retention is respectively 93.4% and 92.8%, improves significantly with respect to the battery in the comparative example.By the made Experimental cell of positive electrode of embodiment 1 preparation, after through 50 circulations, also improve significantly with respect to the battery in the comparative example.
In sum; Utilize aluminium element comparatively cheap, environmental protection to replace nickel and manganese in the nickel manganate cathode material for lithium; Not only help to drop to the cost of material; Can also improve the high temperature of positive electrode and the cycle characteristics under the big electric current effectively, so this system material is a kind of novel high-performance positive electrode.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection range of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (13)
1. a positive electrode that is used for lithium battery is characterized in that, said positive electrode is by general formula LiNi
0.5-xAl
2xMn
1.5-xO
4Expression, in this general formula, 0＜2x≤0.5.
2. positive electrode according to claim 1 is characterized in that, in the said general formula, and 0.1≤2x≤0.2.
3. positive electrode according to claim 2 is characterized in that, in the said general formula, the 2x value is 0.1 or 0.15.
4. the preparation method of a positive electrode as claimed in claim 1 is characterized in that, comprises the steps:
A), adopt the liquid-phase mixing method, manganese source compound, nickel source compound and aluminum source compound are mixed in proportion, obtain mixed solution;
B), said mixed solution is carried out spray drying treatment, obtain first mixture;
C), said first mixture is heat-treated, obtain nickel aluminium Mn oxide precursor;
D), said nickel aluminium Mn oxide precursor and Li source compound are mixed and grind, obtain second mixture;
E), said second mixture is heat-treated, obtain positive electrode.
5. the preparation method of positive electrode according to claim 4 is characterized in that, the mol ratio of nickel, aluminium and manganese is 0.4～0.475: 0.05～0.2 in the said step a): 1.4～1.475.
6. the preparation method of positive electrode according to claim 5 is characterized in that, the mol ratio of nickel aluminium Mn oxide precursor and Li source compound is 0.9～1: 1～1.1 in the said step d).
7. according to the preparation method of any described positive electrode of claim 4 to 6, it is characterized in that heat treated temperature is 700～1000 ℃ in the said step c).
8. the preparation method of positive electrode according to claim 7 is characterized in that, heat treatment period is 10～48h in the said step c).
9. according to the preparation method of any described positive electrode of claim 4 to 6, it is characterized in that heat treated temperature is 500～800 ℃ in the said step e).
10. the preparation method of positive electrode according to claim 9 is characterized in that, heat treatment period is 10～48h in the said step e).
11. the preparation method according to any described positive electrode of claim 4 to 6 is characterized in that, said manganese source compound is a manganese acetate, and said nickel source compound is a nickel acetate, and said aluminum source compound is an aluminum nitrate, and said Li source compound is a lithium hydroxide.
12. a lithium battery anode is characterized in that, comprises matrix and the coating material that places matrix surface, said coating material comprises claim 1 or 2 or 3 described positive electrodes, electric conducting material and binding agent.
13. a lithium battery is characterized in that, comprising: the described lithium battery anode of claim 12, negative pole, be arranged on barrier film and electrolyte between positive pole and the negative pole.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985856A (en) * | 2014-05-16 | 2014-08-13 | 海宁美达瑞新材料科技有限公司 | Nickel cobalt lithium aluminate positive material and preparation method thereof |
| CN105576192A (en) * | 2014-10-14 | 2016-05-11 | 深圳市比克电池有限公司 | Lithium ion battery positive pole material, preparation method of lithium ion battery positive pole material and lithium ion battery |
| CN105655574A (en) * | 2016-04-08 | 2016-06-08 | 广东工业大学 | LiNi0.5Mn1.5O4 cathode material and preparation method thereof |
| CN105655575A (en) * | 2016-04-08 | 2016-06-08 | 广东工业大学 | Lithium-ion battery cathode material and preparation method thereof |
| CN106904588A (en) * | 2017-03-22 | 2017-06-30 | 江苏元景锂粉工业有限公司 | A kind of lithium ion battery with high energy density positive electrode and preparation method thereof |
| CN107230773A (en) * | 2017-05-05 | 2017-10-03 | 个旧圣比和实业有限公司 | Positive electrode for lithium battery and preparation method thereof, lithium battery anode and lithium battery |
| CN113809291A (en) * | 2021-08-11 | 2021-12-17 | 桂林电子科技大学 | Spinel structure positive electrode material of aluminum ion battery and preparation method and application thereof |
-
2011
- 2011-11-28 CN CN2011103847603A patent/CN102394296A/en active Pending
Non-Patent Citations (7)
| Title |
|---|
| 《Journal of Power Sources》 20030410 George Ting-Kuo Fey，et al. Preparation and electrochemical properties of high-voltage cathode materials,LiMyNi0.5-yMn1.5O4(M=Fe,Cu,Al,Mg;y=0.0-0.4) 332-345 1-13 第115卷, 第2期 * |
| 《Solid State Ionics》 20050131 Yasushi Idemoto，et al. Crystal structural change during charge-discharge process of LiMn1.5Ni0.5O4 as cathode material for 5V class lithium secondary battery 299-306 1-13 第176卷, 第3-4期 * |
| 《Solid State Ionics》 20110531 Liping Wang,et al. A comparative study of Fd-3m and P4332 "LiNi0.5Mn1.5O4" 第193卷, * |
| ATSUSHI ITO，ET AL.: "Influence of Co substitution for Ni and Mn on the structural and electrochemical characteristics of LiNi0.5Mn1.5O4", 《JOURNAL OF POWER SOURCES》 * |
| GEORGE TING-KUO FEY，ET AL.: "Preparation and electrochemical properties of high-voltage cathode materials,LiMyNi0.5-yMn1.5O4(M=Fe,Cu,Al,Mg;y=0.0–0.4)", 《JOURNAL OF POWER SOURCES》 * |
| LIPING WANG,ET AL.: "A comparative study of Fd-3m and P4332 "LiNi0.5Mn1.5O4"", 《SOLID STATE IONICS》 * |
| YASUSHI IDEMOTO，ET AL.: "Crystal structural change during charge–discharge process of LiMn1.5Ni0.5O4 as cathode material for 5V class lithium secondary battery", 《SOLID STATE IONICS》 * |
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