CN103413935A - Mo-doped lithium-rich positive electrode material and preparation method thereof - Google Patents
Mo-doped lithium-rich positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Mo-doped lithium-rich positive electrode material and a preparation method thereof. The molecular formula of the Mo-doped lithium-rich positive electrode material is Li(Li0.2Ni0.13Co0.13Mn0.54)0.97Mo0.03O2. The preparation method comprises the following steps: dissolving lithium acetate, cobalt acetate, nickel acetate, manganese acetate and ammonium molybdate in de-ionized water to obtain solution 1 according to the molar ratio of Li:Co:Ni:Mn:Mo being 1.194:0.126:0.126:0.524:0.03; adding citric acid into the de-ionized water to obtain solution 2 according to the ratio of the citric acid molar weight to the total molar weight of Ni, Co, Mn and Mo being 1:1; dropwise adding the solution 2 into the solution 1 and then adjusting pH (potential of Hydrogen) to be 9; stirring at 80 DEG C until purple gel is formed; and performing drying, ball-milling, multi-step calcination and grinding in sequence to obtain the Mo-doped lithium-rich cathode material with high specific discharge capacity, good cycle performance and superior rate performance.
Description
Technical field
The invention belongs to the anode material for lithium-ion batteries preparing technical field, be specifically related to lithium-rich anode material of a kind of Mo of doping and preparation method thereof.
Background technology
As chemical power source, lithium rechargeable battery relies on its high-energy-density and excellent cycle performance to play impetus to the development of new-energy automobile and intelligent grid.And the performances such as the electric weight of positive electrode, voltage are the key factors that determines energy content of battery density, cycle life and security performance.At present, business-like anode material for lithium-ion batteries LiCoO on market
2, LiFePO
4Capacity be respectively 140mAh/g, 160mAh/g, all can not meet the requirement of high-energy-density, the anode material for lithium-ion batteries of therefore developing high power capacity becomes the focus of concern.Lithium-enriched cathodic material of lithium ion battery has superelevation specific capacity (being greater than 250mAh/g), contains less strategic resource Co, so cost is lower and environmental friendliness, has certain potentiality to be exploited.But larger irreversible capacity loss first and poor high rate performance have limited its development and application to a great extent.
Ion doping is to improve one of the multiplying power property of anode material for lithium-ion batteries and effective means of cycle performance.Adulterate micro-metal or nonmetalloid can well improve thermodynamic property and the structural stability of material.For example,, at spinel-type LiNi
0.5Mn
1.5O
4The Ru element of middle trace, significantly improved its specific discharge capacity under high magnification; F
-Ion doping can replace the oxonium ion of part, has suppressed separating out of oxygen element, can improve the cycle performance of material.Because the interaction between doping ion and matrix is very complicated, doping vario-property also needs further experimental study to the mechanism of action that material electrochemical performance exerts an influence.
Simultaneously, the preparation method is the key factor that affects the lithium-enriched cathodic material of lithium ion battery performance.Lithium-rich anode material such as Li
1.2Ni
0.175Co
0.1Mn
0.525O
2, Li
1.2Ni
0.2Mn
0.6O
2Deng, the most frequently used preparation method is solid reaction process, but uses the standby material of this legal system can not reach mixed uniformly level, and easily introduces impurity in the process of preparation.Therefore, can adopt some other softening method to improve the chemical property of material, generally comprise sol-gel process, spray drying process, hydro thermal method etc.Wherein, sol-gal process prepares positive electrode, and to have a chemical uniformity good, narrow diameter distribution, the advantage such as purity is high, and grain diameter is little.But also exist some shortcomings:
(1) in preparation process, often need to consume a large amount of more expensive organic acid or alcohol, cost is higher, is unsuitable for large-scale production.(2) whole preparation process needs the ageing process of long period, and time cost is too high.(3) when presoma is calcined, traditional calcine technology adopts the one-step calcination method, and calcination time is long, is generally 20h, therefore the energy is produced to waste.
Summary of the invention
One of purpose of the present invention is in order to solve the above-mentioned poor defect of lithium-rich anode material high rate performance, and a kind of lithium-rich anode material of the doping Mo of high rate performance and cycle performance preferably that has is provided.
Two of purpose of the present invention is high in order to solve in above-mentioned lithium-rich anode material preparation method existing production cost; be unsuitable for large-scale production; technical problems such as calcination time is long, energy waste and provide that a kind of production cost is low, calcination time is short, be suitable for the preparation method of lithium-rich anode material of the doping Mo of the characteristics such as large-scale production.
Know-why of the present invention
Take lithium acetate, cobalt acetate, nickel acetate, manganese acetate and ammonium molybdate is raw material, and citric acid is the precursor of the chelating agent lithium-rich anode material that synthesized doping Mo by calcine by steps obtain the adulterating lithium-rich anode material of Mo.
Technical scheme of the present invention
The lithium-rich anode material of a kind of Mo that adulterates, its molecular formula are Li (Li
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2.
The preparation method of the lithium-rich anode material of above-mentioned a kind of Mo that adulterates, namely
At first, calculate in molar ratio, be that Li:Co:Ni:Mn:Mo is the ratio of 1.194:0.126:0.126:0.524:0.03, lithium acetate, cobalt acetate, nickel acetate, manganese acetate and ammonium molybdate are dissolved in deionized water, obtain solution 1, in actual fabrication process, lithium acetate used is excessive 5%, the loss of lithium when making up follow-up calcining;
Calculate in molar ratio, namely the integral molar quantity of the mole of citric acid: Ni, Co, Mn and Mo is the ratio of 1:1, and citric acid is joined in deionized water, obtains solution 2;
Then, it is 2ml/min that solution 2 is controlled to drop rate, is added drop-wise to solution 2 in solution 1 and, after mixing, uses ammoniacal liquor, and preferably with the ammoniacal liquor that mass percentage concentration is 28%, regulating pH is 9, under 80 ℃ of conditions, continues to stir until form purple gel;
Then, the ball milling purple gel of above-mentioned gained is dried under 200 ℃ after, obtain the precursor pressed powder;
Finally, the precursor pressed powder of above-mentioned gained is carried out to calcine by steps, grind after calcining, the lithium-rich anode material of the Mo that must adulterate.
Lithium-rich anode material Li (the Li of above-mentioned a kind of Mo that adulterates
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2The preparation method, specifically comprise the steps:
(1), calculate in molar ratio, be that Li:Co:Ni:Mn:Mo is that the ratio of 1.194:0.126:0.126:0.524:0.03 is by lithium acetate, nickel acetate cobalt acetate and manganese acetate and ammonium molybdate, be dissolved in deionized water, form solution 1, in actual mechanical process, lithium acetate is excessive 5%, the loss of lithium when making up follow-up calcining;
(2), in molar ratio calculate, namely the ratio of the integral molar quantity of the mole of citric acid: Ni, Co, Mn and Mo is 1:1, using citric acid as chelating agent, is dissolved in deionized water, forms solution 2;
(3), the control drop rate is 2ml/min, and solution 2 is dropwise added in solution 1, then uses ammoniacal liquor, being preferably and regulating pH with the ammoniacal liquor that mass percentage concentration is 28% is 9, controlling temperature is under 80 ℃ of conditions, to continue to stir until form purple gel;
(4), the purple gel of gained is carried out to ball milling after under 200 ℃, drying, obtain the precursor pressed powder;
(5), the precursor pressed powder of step (4) gained is controlled to temperature be 400 ℃ and carry out precalcining 4h, then the speed with 5 ℃/min is warming up to 900 ℃ of calcining 8h, after calcining, grinds fully the lithium-rich anode material of the Mo that must adulterate.
Beneficial effect of the present invention
The lithium-rich anode material of a kind of Mo that adulterates of the present invention, have the superelevation specific capacity, low range, and namely under the 0.2C multiplying power, the residual capacity circulated after 50 times is 252.0Amh/g, has fully shown the characteristic of high power capacity.At high magnification, be under the 5C multiplying power, first discharge specific capacity is up to 158.2mAh/g, the residual capacity circulated after 50 times is 152.7mAh/g, irreversible capacity loss is only 5.5mAh/g, capability retention, up to 96.5%, shows thus, and the lithium-rich anode material of a kind of Mo of doping of the present invention has excellent high rate performance and cycle performance.
Further, the preparation method of the lithium-rich anode material of a kind of Mo that adulterates of the present invention, in preparation process due to the novel sol-gal process adopted under the certain material proportioning, namely utilize lithium acetate, cobalt acetate, nickel acetate and manganese acetate and ammonium molybdate to be raw material, citric acid is the lithium-rich anode material Li (Li that chelating agent has synthesized doping Mo
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2Precursor, and by the lithium-rich anode material Li (Li of novel calcine technology preparation doping Mo
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2, as its well-formed of electrode material, grain diameter is little, is only 100-300nm, and is evenly distributed, and battery performance is good.
Further, the preparation method of the lithium-rich anode material of a kind of Mo that adulterates of the present invention, owing to having added the organic acid citric acid as chelating agent, each raw material is evenly mixed in the molecule rank, have chemical uniformity good, the presoma narrow diameter distribution of final gained, purity is high, the advantages such as grain diameter is little, be conducive to follow-up calcination process.
Further, the preparation method of the lithium-rich anode material of a kind of Mo that adulterates of the present invention, compare with traditional sol-gal process, this method adopts citric acid as chelating agent, its consumption is only traditional 40%, greatly reduces production cost, is conducive to realize large-scale production.
Further, the preparation method of the lithium-rich anode material of a kind of Mo that adulterates of the present invention, owing to adopting magnetic agitation, only need 4h just can obtain purple gel shape material, obtains the required digestion time of gel thereby reduced, and improved production efficiency.
Further, the preparation method of the lithium-rich anode material of a kind of Mo that adulterates of the present invention, owing to adopting calcine by steps, namely control temperature and be 400 ℃ and carry out precalcining 4h in high temperature process furnances, and then the speed with 5 ℃/min is warming up to 900 ℃ of calcining 8h.With traditional calcine technology, compare, its calcination time is only traditional 60%, thereby has reduced the loss of the energy, has also further reduced production cost.
In sum, the preparation method of the lithium-rich anode material of a kind of Mo that adulterates of the present invention, production cost is low, production efficiency is high, is conducive to realize large-scale production, and the lithium-rich anode material capacity of the doping Mo of gained is higher, low range, be under the 0.2C multiplying power, the residual capacity circulated after 50 times is 252.0Amh/g, has fully shown the characteristic of high power capacity.At high magnification, namely under the 5C multiplying power, first discharge specific capacity is up to 158.2mAh/g, the residual capacity circulated after 50 times is 152.7mAh/g, irreversible capacity loss is only 5.5mAh/g, and capability retention, up to 96.5%, has high rate performance and cycle performance preferably.As its well-formed of electrode anode material, grain diameter is little, is evenly distributed, and battery performance is good.
The accompanying drawing explanation
Lithium-rich anode material Li (the Li of Fig. 1, embodiment 1 gained doping Mo
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2The XRD picture;
Lithium-rich anode material Li (the Li of Fig. 2, embodiment 1 gained doping Mo
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2Multiplication factor is the SEM picture obtained under 10000 times;
Lithium-rich anode material Li (the Li of Fig. 3, doping Mo
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2Be assembled into the 3 times cyclic voltammetry curve after experimental button cell, sweep limits be 2.5V to 4.8V, sweep speed is 0.1mV/s;
Lithium-rich anode material Li (the Li of Fig. 4, doping Mo
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2After being assembled into experimental button cell, front 50 charging and discharging capacities under the 0.2C multiplying power and enclosed pasture efficiency curve;
Lithium-rich anode material Li (the Li of Fig. 5, doping Mo
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2After being assembled into experimental button cell, the first with 50th charging and discharging capacity curve under the 0.2C multiplying power;
Lithium-rich anode material Li (the Li of Fig. 6, doping Mo
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2After being assembled into experimental button cell, the cycle performance curve under 0.2C, 0.5C, 1C, 2C, 5C multiplying power respectively.
Embodiment
Below by specific embodiment, also by reference to the accompanying drawings the present invention is further set forth, but do not limit the present invention.
The lithium-rich anode material of a kind of Mo that adulterates, its molecular formula are Li (Li
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2.
Lithium-rich anode material Li (the Li of above-mentioned a kind of Mo that adulterates
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2The preparation method, specifically comprise the steps:
(1), by the 3.1975g lithium acetate, the 0.8047g cobalt acetate, the 0.8039g nickel acetate, 3.1710g manganese acetate and 0.1508g ammonium molybdate are dissolved in deionized water, form solution 1;
The amount of above-mentioned lithium acetate, nickel acetate cobalt acetate and manganese acetate and ammonium molybdate used is pressed the mol ratio of Li:Co:Ni:Mn:Mo and is calculated, and namely the mol ratio of Li:Co:Ni:Mn:Mo is 1.2537:0.126:0.126:0.524:0.03;
Wherein lithium acetate used is excessive 5%, the loss of lithium when making up follow-up calcining;
(2), by the 4.2028g citric acid, be dissolved in deionized water, form solution 2;
The amount of above-mentioned citric acid used, calculate in molar ratio, i.e. the mole of citric acid: the ratio of the integral molar quantity of transition metal ions Ni, Co, Mn and Mo is 1:1;
(3), the control drop rate is 2ml/min, and solution 2 is added drop-wise in solution 1, then with the ammoniacal liquor that mass percentage concentration is 28%, regulating pH is 9, under 80 ℃ of conditions, continues to stir 4h, until form purple gel;
(4), the purple gel of step (3) gained is put into to baking oven, at 200 ℃, dry 12h, in the process of oven dry, gel can be expanded to spherical gradually, its volume is the several times of gel, obtains precursor solid transfer to ball milling in ball mill and obtains the precursor pressed powder;
(5), the precursor pressed powder of step (4) gained being controlled to temperature in the high-temperature tubular furnace system is 400 ℃ and carries out precalcining 4h, then the speed with 5 ℃/min is warming up to 900 ℃ of calcining 8h, material after calcining is ground to particle diameter in mortar be 100-300nm, the lithium-rich anode material Li (Li of the Mo that must adulterate
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2.
Lithium-rich anode material Li (Li by the doping Mo of above-mentioned gained
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2Utilize X-ray diffractometer (D8-ADVANCE type, Germany Bruker company produces) scanning, scanning result as shown in Figure 1, as can be seen from Figure 1, it is sharp-pointed that it goes out peak, (006) it is obvious that/(012) and (108)/(110) split peak, (003) ratio to (104) peak strength
I (003)/
I (104)Be greater than 1.2, shown thus the lithium-rich anode material Li (Li of embodiment 1 gained
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2Has good layer structure.
Lithium-rich anode material Li (the Li of the doping Mo of above-mentioned gained
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2By scanning electron microscopy (JSM-5900 type, Japanese JEOL company produces), observe, its multiplication factor be SEM figure of obtaining under 10000 times as shown in Figure 2; As seen from Figure 2, the lithium-rich anode material Li (Li of the doping Mo of embodiment 1 gained
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2Particle is spherical and is evenly distributed, without obvious agglomeration.
Application Example 1
Lithium-rich anode material Li (Li by the doping Mo of embodiment 1 gained
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2Be assembled into experimental button cell, number of assembling steps is as follows:
1, the preparation of anode pole piece
Lithium-rich anode material Li (Li by the doping Mo of embodiment 1 gained
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2, conductive agent Super-p and binding agent PVDF be that the ratio of 80:10:10 is mixed in mass ratio, then be placed on magnetic stirring apparatus and stir into uniform sizing material, evenly coat on aluminium foil, after 100 ℃ of air drying 2h, making diameter is the circular anode pole piece of 14mm;
2, the preparation of battery cathode
In dry glove box, scrape off high-purity lithium sheet surface oxide layer, the metal surface of exposing gloss namely obtains battery cathode;
3, experimental button cell assembling
In being full of the vacuum glove box of argon gas, be assembled into CR2016 type button cell.Electrolyte is LiPF
6/ EC (ethylene carbonate)+DMC (dimethyl carbonate) (volume ratio is 1:1), metal lithium sheet is as battery cathode, and barrier film is the Celgard2400 polypropylene film.In CR2016 type Snap-type cell positive shell, put into anode pole piece, barrier film is covered on anode pole piece, after dripping electrolyte, by metal lithium sheet, be that battery cathode is placed on barrier film gently again, put into again the nickel foam as backing material, the battery cathode cap, to anode cover, and then is assembled into to CR2016 type experimental button cell.
The CR2016 type experimental button cell prepared is connected on the CHI660C electrochemical workstation, and work electrode connects anode, and reference electrode and be lithium metal to electrode carries out cyclic voltammetry, and concrete outcome is shown in Fig. 3.
Fig. 3 is the lithium-rich anode material Li (Li of the doping Mo of embodiment 1 gained
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2Be assembled into the 3 times cyclic voltammetry curve after experimental button cell, sweep limits be 2.5V to 4.8V, sweep speed is 0.1mV/s.
As can be seen from Figure 3, cyclic process for the first time is namely in the represented cyclic voltammetry curve of the 1st in figure, and near the oxidation peak 4.5V disappears in circulation subsequently, illustrates in the lithium-rich anode material of doping Mo in charge and discharge process for the first time Li has occurred
2MnO
3The activation of component, lithium layer and transition metal layer be de-Li jointly
+, the oxygen that is accompanied by lithium layer both sides is also deviate from jointly, has namely deviate from Li
2O.Li
2MnO
3Become LiMnO
2.And namely the represented cyclic voltammetry curve of the 3rd in figure is substantially overlapping in the i.e. represented cyclic voltammetry curve of 2nd in figure and the cyclic process for the third time of later cyclic process for the second time that circulate for the first time, the lithium-rich anode material invertibity of doped with Mg that above-mentioned gained is described is good, in this discharged and recharged interval, the electro-chemical activity of the lithium-rich anode material of doping Mo was good.
Lithium-rich anode material Li (the Li of the doping Mo of embodiment 1 gained
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2Battery performance by the assembling after CR2016 type button cell, on LAND battery test system CT2001A, test, adopt respectively the different multiplying condition to test.Test result is shown in Fig. 4, Fig. 5 and Fig. 6.
Fig. 4 is the lithium-rich anode material Li (Li of the doping Mo of embodiment 1 gained
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2Be assembled into front 50 the charge and discharge specific capacities under the 0.2C multiplying power and an enclosed pasture efficiency curve after experimental button cell, the curve 1 in Fig. 4 is the charge ratio capacity of first 50 times, and curve 2 is the specific discharge capacity of first 50 times, and curve 3 is the enclosed pasture efficiency of first 50 times.As can be seen from Figure 4,0.2C discharges and recharges the lithium-rich anode material Li (Li of the doping Mo of embodiment 1 gained under condition
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2The residual capacity circulated after 50 times is 252.0Amh/g, has fully shown the characteristic of high power capacity.
Fig. 5 is the lithium-rich anode material Li (Li of the doping Mo of embodiment 1 gained
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2Be assembled into the first with 50th charging and discharging capacity under the 0.2C multiplying power after experimental button cell.In Fig. 5,1 for charging curve first, 2 for discharge curve, 3 first be that the 50th charging curve, 4 is the 50th discharge curve.From the initial charge curve Fig. 5, can find out, there is obvious 4.5V high-voltage charge platform in the lithium-rich anode material of embodiment 1 gained doping Mo, after 50 circulations, its residual capacity is 252.0Amh/g, has shown that thus the battery performance of lithium-rich anode material of doping Mo of embodiment 1 gained is good.
Fig. 6 is the lithium-rich anode material Li (Li of the doping Mo of embodiment 1 gained
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2Be assembled into after experimental button cell the cycle performance curve under 0.2C, 0.5C, 1C, 2C, 5C multiplying power respectively.From the cycle performance curve of Fig. 6, can find out, along with the increase of charge-discharge magnification, the specific discharge capacity of battery descends to some extent.At high magnification, namely under the 5C multiplying power, first discharge specific capacity is up to 158.2mAh/g, and the residual capacity circulated after 50 times is 152.7mAh/g, and irreversible capacity loss is only 5.5mAh/g, and capability retention, up to 96.5%, has shown good high rate performance.
In sum, the lithium-rich anode material Li (Li of the doping Mo of a kind of gained provided by the invention
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2Have that specific discharge capacity is high, cycle performance is excellent, the advantage that production cost is low.Further, the preparation method of the lithium-rich anode material of doping Mo of the present invention is because amount of chelant is few, and calcining heat is low and the time is short, and the consumption that therefore can save raw-material consumption and reduce the energy, be conducive to realize industrial-scale production.
The above is only giving an example of embodiments of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (5)
1. the lithium-rich anode material of the Mo that adulterates, is characterized in that the molecular formula of the lithium-rich anode material of described doping Mo is Li (Li
0.2Ni
0.13Co
0.13Mn
0.54)
0.97Mo
0.03O
2.
2. the preparation method of the lithium-rich anode material of doping Mo as claimed in claim 1, is characterized in that comprising the steps:
At first, calculate in molar ratio, namely Li:Co:Ni:Mn:Mo is the ratio of 1.194:0.126:0.126:0.524:0.03, and lithium acetate, cobalt acetate, nickel acetate, manganese acetate and ammonium molybdate are dissolved in deionized water, obtains solution 1;
Calculate in molar ratio, namely the integral molar quantity of the mole of citric acid: Ni, Co, Mn and Mo is the ratio of 1:1, and citric acid is joined in deionized water, obtains solution 2;
Then, it is 2ml/min that the solution of above-mentioned gained 2 is controlled to drop rate, is added drop-wise to solution 2 in solution 1 and after mixing, with ammoniacal liquor, regulating pH is 9, under 80 ℃ of conditions, continues to stir until form purple gel;
Then, the ball milling purple gel of above-mentioned gained is dried under 200 ℃ after, obtain the precursor pressed powder;
Finally, the precursor pressed powder of gained is carried out to calcine by steps, grind after calcining, the lithium-rich anode material of the Mo that must adulterate.
3. the preparation method of the lithium-rich anode material of a kind of Mo that adulterates as claimed in claim 2, is characterized in that at first described calcine by steps namely control temperature and be 400 ℃ and carry out precalcining 4h, and then the speed with 5 ℃/min is warming up to 900 ℃ of calcining 8h.
4. the preparation method of the lithium-rich anode material of a kind of Mo that adulterates as claimed in claim 2, is characterized in that described ammoniacal liquor, and its mass percentage concentration is 28%.
5. the preparation method of the lithium-rich anode material of a kind of Mo that adulterates as claimed in claim 2, is characterized in that lithium acetate used in preparation process excessive 5%.
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| CN104900857A (en) * | 2015-06-02 | 2015-09-09 | 上海电力学院 | Preparation method of trace Mo-doped lamellar lithium-enriched ternary positive electrode material |
| CN106532037A (en) * | 2017-01-13 | 2017-03-22 | 哈尔滨工业大学 | Preparation method of vanadium-molybdenum-doped lithium ion battery cathode material |
| CN107768664A (en) * | 2017-10-23 | 2018-03-06 | 广东工业大学 | A kind of lithium-rich manganese-based anode material of molybdenum doping and preparation method thereof |
| CN107994226A (en) * | 2017-12-14 | 2018-05-04 | 桑顿新能源科技有限公司 | A kind of lithium-rich anode material of Mn adulterated lithium manganate and preparation method thereof |
| CN111224095A (en) * | 2018-11-23 | 2020-06-02 | 三星电子株式会社 | Composite positive active material, method for preparing same, positive electrode comprising composite positive active material, and lithium battery comprising positive electrode |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102354741A (en) * | 2011-09-09 | 2012-02-15 | 中国科学院宁波材料技术与工程研究所 | Preparation method of high-capacity layered lithium-rich manganese-based oxide |
-
2013
- 2013-08-27 CN CN2013103785305A patent/CN103413935A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102354741A (en) * | 2011-09-09 | 2012-02-15 | 中国科学院宁波材料技术与工程研究所 | Preparation method of high-capacity layered lithium-rich manganese-based oxide |
Non-Patent Citations (1)
| Title |
|---|
| 杜运等: ""层状正极材料Li[Li0.2 Mn0.54Ni0.13Co0.13-xAlx]O2的合成及其电化学性能研究"", 《化工新型材料》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104900857A (en) * | 2015-06-02 | 2015-09-09 | 上海电力学院 | Preparation method of trace Mo-doped lamellar lithium-enriched ternary positive electrode material |
| CN106532037A (en) * | 2017-01-13 | 2017-03-22 | 哈尔滨工业大学 | Preparation method of vanadium-molybdenum-doped lithium ion battery cathode material |
| CN107768664A (en) * | 2017-10-23 | 2018-03-06 | 广东工业大学 | A kind of lithium-rich manganese-based anode material of molybdenum doping and preparation method thereof |
| WO2019080310A1 (en) * | 2017-10-23 | 2019-05-02 | 广东工业大学 | Molybdenum-doped lithium-rich manganese-based cathode material and preparation method therefor |
| CN107994226A (en) * | 2017-12-14 | 2018-05-04 | 桑顿新能源科技有限公司 | A kind of lithium-rich anode material of Mn adulterated lithium manganate and preparation method thereof |
| CN111224095A (en) * | 2018-11-23 | 2020-06-02 | 三星电子株式会社 | Composite positive active material, method for preparing same, positive electrode comprising composite positive active material, and lithium battery comprising positive electrode |
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