CN102790213A - Manufacturing method of spherical lithium battery anode material lithium/carbon manganese phosphate - Google Patents
Manufacturing method of spherical lithium battery anode material lithium/carbon manganese phosphate Download PDFInfo
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- CN102790213A CN102790213A CN2012102659832A CN201210265983A CN102790213A CN 102790213 A CN102790213 A CN 102790213A CN 2012102659832 A CN2012102659832 A CN 2012102659832A CN 201210265983 A CN201210265983 A CN 201210265983A CN 102790213 A CN102790213 A CN 102790213A
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Abstract
The invention discloses a manufacturing method of a spherical lithium battery anode material lithium/carbon manganese phosphate, which comprises the steps as follows: acquiring, evenly mixing and dispersing a lithium source, a phosphorus source, a manganese source and a carbon source, and obtaining an evenly dispersed precursor solution via stirring; and executing spraying and drying for the precursor solution, obtaining precursor powder, executing heat treatment of the precursor powder, and obtaining spherical lithium battery anode material lithium/carbon manganese phosphate after the precursor powder is cooled at a room temperature. The manufacturing method improves mixing evenness of raw materials via a material manufactured by applying a spraying and drying combination process, shortening a reaction process is facilitated, the process is simple and easy to control, no pollution is generated, the cost is low, time consumption is short, grain size of the manufactured lithium battery anode material lithium/carbon manganese phosphate is evenly distributed, and the grain diameter is micron-grade.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of preparation method of ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon.
Background technology
Since 21 century; Energy crisis and environmental pollution have become two stern challenges that human social faces; Therefore; Tapping a new source of energy is the key technology that be badly in need of to solve 21 century, and the development of a chemical power source importance of new energy development just has important practical sense to solving energy crisis and problem of environmental pollution.Wherein, Lithium ion battery is because advantage such as the current potential platform is high, energy density is high, long service life, environmental pollution are little, as one type of important chemical cell, kept fast-developing since hauling oneself willingly into market always; Occupied very big share in small-sized secondary batteries market; And more and more under the serious situation, the development electric automobile is as the vehicles in global environment and energy problem, and lithium ion battery is considered to the choosing of ideal as the major impetus source.
Propose transition metal phosphate system positive electrode first from Goodenough in 1997,, just caused people's extensive concern once appearance.LiMPO
4(M=Mn, Fe, Co, Ni) serial electrode material belongs to polyanion type compound, has olivine structural, and higher specific capacity, low cost, advantages of environment protection are arranged.Wherein, LiFePO
4Be to study one of focus at present, but its current potential platform is lower, causes its energy density lower, and Co
2+/ Co
3+, Ni
2+/ Ni
3+Chemical potential be respectively 4.8V and 5.1V, higher voltage can cause the decomposition of electrolyte, influences the fail safe of battery, the electrolyte that uses at present can't bear very high voltage, to LiNiPO
4And LiCoPO
4That studies is less, LiMnPO in these materials
4With respect to Li
+/ Li electrode potential is 4.1V, with LiCoO
2Quite, be positioned at existing electrolyte system and stablize electrochemical window, and theoretical specific capacity there is 170mAh/g, LiMnPO
4Have low price, output voltage is high, and security performance is good, environmental friendliness, and if potential advantages such as high-energy-density are LiMnPO
4Actual capacity perform to and LiFePO
4Identical degree, its energy density will compare LiFePO
4High by 35%, yet, LiMnPO
4Have inevitable shortcoming as positive electrode, employings such as YAMADA first principle calculates electron energy level, LiMnPO
4Electronic conductivity lower, belong to insulator, and, Li
+At LiMnPO
4In diffusion admittance be one dimension, thereby diffusion velocity is slow, makes material high rate charge-discharge poor-performing, the utilance of active material is on the low side, if can overcome the intrinsic shortcoming of material, LiMnPO so
4It will be a very potential positive electrode.
At present, LiMnPO
4The preparation method comprise solid phase method, sol-gal process, coprecipitation, hydro thermal method, solvent-thermal method and polyalcohol method etc., the emerging seminar of domestic Li Xinhai of Central South University and Wang Zhi adopts solid phase method, with Li
2CO
3, MnCO
3, NH
4H
2PO
4Be raw material, mix with an amount of carbon black, first ball milling 36h, 300 ℃ of pre-burning 3h take out intermediate product and continue ball milling 24h, and 600 ℃ of calcining 24h obtain the olivine structural LiMnPO of pure phase
4, discharge capacity is 100mAh/g, but this method product particle size distribution is inhomogeneous, and power consumption is big, and generated time is longer, and people such as Nam-Hee Kwon use sol-gal process, and adopting lithium acetate, manganese acetate and ammonium dihydrogen phosphate is raw material, and complexing agent is a glycolic, through HNO
3Regulate pH value and make less than 4,520 ℃ and 570 ℃ of calcinings, the particle size that makes is 140 ~ 160nm with the precursor powder that obtains; 0.01C specific discharge capacity is 156mAh/g, the 0.1C reversible capacity is 134mAh/g, and granular size has been discussed to effect of material performance; The alkoxide that this method is used is harmful, and there is pollution a large amount of synthesizing to environment, and price is higher; The processing cycle is longer, and the commercial production difficulty is bigger.People such as Haisheng Fang are through hydrothermal synthesis method, with Li
2SO
4H
2O, MnSO
4H
2O and NH
4H
2PO
4Be raw material, successfully synthesize bar-shaped LiMnPO
4Material is evenly distributed, and length about 1 μ m is arranged, and discharging and recharging cut-ff voltage is 3-4.5V, and the 0.01C reversible capacity is 68mAh/g, and has better cycle performance.With the aqueous solution in the hydro-thermal reaction, change organic solvent into as reaction medium, obtain the solvent thermal building-up reactions method; People such as Yang use solvent thermal process, according to stoichiometric proportion, with a hydronium(ion) oxidation lithium; Phosphoric acid, Manganous sulfate monohydrate, hexadecane trimethyl ammonium bromide (CTAB) mixing is dissolved in the methanol mixed solvent; 240 ℃ of heating 12h obtain white LiMnPO after the cooling in autoclave
4Deposit with after glucose mixes, at 700 ℃ of calcinings of Ar gas shiled 5h, obtains LiMnPO with deposit
4/ C material.According to present existing report, hydro-thermal and solvent thermal are synthesized LiMnPO
4Material is still the comparison difficulty, though liquid-phase synthesis process can reach the molecular level level, operation is had relatively high expectations, and produces the operation trouble in enormous quantities, has limited its application.
Summary of the invention
Technical problem of the present invention provides a kind of preparation method of ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon; This preparation method's technology is simple and easy to control; Pollution-free, cost is low, and weak point consuming time; The lithium ion battery anode material manganese lithium phosphate for preparing/carbon granule even size distribution, particle diameter can reach micron order.
Above-mentioned technical problem of the present invention can realize through following technical scheme: a kind of preparation method of ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon; Contain following steps: after getting lithium source, phosphorus source, manganese source and carbon source mixing; Be scattered in the liquid medium, obtain finely dispersed precursor solution through stirring; Temperature when regulating spray drying is 220 ℃ ~ 270 ℃; Feed rate is 300 ~ 500mL/h; Nozzle diameter is 0.5 ~ 2mm, and atomizing pressure is 0.2 ~ 0.4MPa, and precursor solution is carried out spray drying; Obtain precursor powder; Precursor powder is heat-treated, and heat treatment is that 1 ~ 10 ℃/min is warming up to 400 ℃ ~ 600 ℃ precursor powder carried out calcination process 3 ~ 20h with heating rate under the protective gas effect, obtains ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon through being cooled to room temperature.
Technique scheme of the present invention utilizes spray drying to combine heat treated mode to prepare lithium ion battery anode material manganese lithium phosphate/carbon; Improved the uniformity of raw materials mix; Help shortening course of reaction; Can prepare particle size distribution uniform spherical olivine structural lithium manganese phosphate material, thereby improve the chemical property of lithium manganese phosphate positive electrode.
Concrete, the preparation method of above-mentioned ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon can may further comprise the steps:
(1) precursor solution preparation: after lithium source, phosphorus source and manganese source and carbon source mixed by stoichiometric proportion, be dissolved in the liquid medium, under magnetic agitation, constantly stir, solution is uniformly dispersed;
(2) precursor powder preparation: with the solution that mixes,, under certain baking temperature, nozzle diameter, feed rate, atomizing pressure, carry out spray drying, make precursor powder through spray drying device;
(3) calcination process: precursor powder is placed in the porcelain boat, with certain heating rate, in protective gas calcining down, naturally cools to room temperature, obtaining carbon coating lithium manganese phosphate particulate is ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon granule.
Among the present invention in lithium source, phosphorus source and the manganese source mol ratio of lithium, phosphorus, manganese be preferably 1 ︰, 1 ︰ 1; The consumption of carbon source preferably accounts for 6 ~ 15% of lithium source, phosphorus source and manganese source total weight.
The quality percentage composition of carbon is preferably 1 ~ 10% in the carbon source of the present invention.
Lithium according to the invention source is preferably one or more in lithium acetate, lithium chloride, lithium sulfate, lithium nitrate and the lithium dihydrogen phosphate; Said phosphorus source is preferably one or more in phosphoric acid, ammonium dihydrogen phosphate and the lithium dihydrogen phosphate; Said manganese source is preferably one or more in manganese acetate, manganese nitrate, manganese sulfate and the manganese chloride; Said carbon source is preferably one or more in phenolic resins, sucrose, citric acid, glucose, ascorbic acid, cellulose, polyvinylpyrrolidone and the polyethylene glycol.
Liquid medium according to the invention is preferably water, ethanol, acetone, water-ethanol solution, ethylene glycol or polyethylene glycol.
Protective gas according to the invention is preferably mist or the mist of nitrogen and argon gas of mist, argon gas and the hydrogen of nitrogen, nitrogen and hydrogen, and wherein the volumn concentration of hydrogen is preferably 2 ~ 10% in the mist of argon gas and hydrogen.
Heat treatment of the present invention is that 1 ~ 10 ℃/min is warming up to 400 ℃ earlier precursor powder carried out calcination process 2 ~ 5h with heating rate preferably under the protective gas effect, continues to be preferably 1 ~ 10 ℃/min with heating rate again and is warming up to 600 ℃ precursor powder carried out the preferred 1 ~ 15h of calcination process.
The present invention can reach micron order through being cooled to room temperature acquisition ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon, mainly is the primary particle of being reunited and being formed by second particle, and the size of this primary particle is 3 ~ 10 μ m.
Compared with prior art, the present invention has following advantage:
(1) the present invention has improved the uniformity of raw materials mix through the material that spray drying combines heat treatment process to prepare, and helps shortening course of reaction;
(2) preparation method of ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon of the present invention, technology is simple and easy to control, and is pollution-free, and cost is low, and the cycle is short;
(3) the manganese phosphate lithium/carbon composite material that makes of the present invention, particle size distribution is even, and is spherical olivine structural, and by the primary particle that second particle is reunited and formed, size is that 3 ~ 4 μ m are in the majority;
(4) adopt lithium manganese phosphate of the present invention/carbon positive electrode to have the discharge voltage about 4V, first discharge specific capacity can reach 115mAh/g under 25 ℃, 0.1C multiplying power, and has excellent cyclical stability;
(5) lithium manganese phosphate/carbon positive electrode energy density that adopts the inventive method to obtain is high, and chemical property is good, is easy to realize the suitability for industrialized production that cleans.
Description of drawings
Fig. 1 is the sem photograph (SEM) of embodiment 1 sample;
Fig. 2 be the lithium manganese phosphate of embodiment 1 preparation under the 0.1C multiplying power, 2.0-4.5V discharges and recharges electric curve;
Fig. 3 be the lithium manganese phosphate of embodiment 1 preparation under the 0.2C multiplying power, the capacity cycle performance curve that 2.0-4.5V discharges and recharges;
Fig. 4 be the lithium manganese phosphate of embodiment 1 preparation under the 0.1C-2C multiplying power, 2.0-4.5V charge-discharge magnification performance map.
Embodiment
Embodiment 1
(1) precursor solution preparation: with 6.183g LiAC2H
2O, 14.853g Mn (AC)
24H
2O, 6.971gNH
4H
2PO
4(mol ratio of lithium, manganese, phosphorus is 1:1:1); 2.763g citric acid (through calculating, in the citric acid quality of carbon be raw materials quality 10%) be dissolved in the water, be configured to 300mL solution; Make that ion concentration is 0.2mol/L, constantly stirring makes raw materials mix even under magnetic agitation;
(2) precursor powder preparation: with the mixed solution of preparation, at 220 ℃ of baking temperatures, nozzle diameter 2mm, feed rate 400mL/h, atomizing pressure 0.3MPa carries out spray drying, obtains precursor powder;
(3) heat treatment: get a certain amount of precursor powder and be placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming; At first the speed with 2 ℃/min is warming up to 400 ℃ of maintenance 2h with mixture; And then be heated to 600 ℃ with 5 ℃/min speed and keep 12h; Naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, the lithium manganese phosphate that obtains the carbon coating is ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon;
Spray drying makes shown in the sem photograph such as Fig. 1 a of precursor powder; Material has spherical morphology, and particle size is about 5 μ m, and the SEM figure of the lithium manganese phosphate/carbon that obtains after the roasting is shown in Fig. 1 b; Lithium manganese phosphate after the roasting/carbon primary particle is reunited by second particle and is formed; Particle diameter is 3 ~ 4 μ m, has spherical morphology, even size distribution.
With the above-mentioned material sample that makes, conductive agent acetylene black, binding agent PVDF ratio according to mass ratio 75:20:5; Making solvent with N-methyl pyrrolidone NMP is applied on the Al paper tinsel after evenly; Behind 110 ℃ of dry 2h; On the particulate tablet press machine, make positive plate with 15MPa pressure compressing tablet, simulated battery is assembled in the glove box of argon shield and carries out, and negative pole is a metal lithium sheet.Experimental technique is: with 0.1C rate charge-discharge 5 times, carry out charge-discharge test with the 0.2C multiplying power again, charging/discharging voltage is 2.0-4.5V, tests first capacity, maximum discharge capacity, enclosed pasture efficient and the capability retention after 30 weeks of circulating first.
The lithium manganese phosphate material is as shown in Figure 2 with the first charge-discharge curve under the 0.1C multiplying power, and charging/discharging voltage is 2.0-4.5V, and discharge capacity is 115.4mAh/g first; Enclosed pasture efficient is 80% first, and the cycle performance of lithium manganese phosphate material under the 0.2C multiplying power is as shown in Figure 3, and the trend of decay is arranged with circulation volume; But all in all, the material cycle performance is better, and discharge capacity is 88.3mAh/g first; Capacity behind circulation 30 circles is 85.3mAh/g, and capability retention is 96.6%, and institute's synthetic material is decayed bigger under the 0.1C multiplying power; Charge/discharge capacity is bigger under low range though this is; But also can cause bigger structural volume to change simultaneously, therefore, under low range, have more serious capacitance loss and take place.
The high rate performance of material is as shown in Figure 3, because polarization, discharge capacity increases with multiplying power and reduces, and the 1C discharge capacity has 50.7mAh/g, and the 2C discharge capacity still has 41.3mAh/g; Discharge and recharge with the 0.1C multiplying power after the 2C rate charge-discharge, capacity is 98.mAh/g, can return to the capacity under the initial 0.1C multiplying power, shows that material has high rate performance preferably again.
Above-mentioned experimental data shows that ball-shaped lithium-ion battery anode material lithium manganese phosphate/material with carbon element chemical property that the present invention prepares is good.
Embodiment 2
(1) precursor solution preparation: with 6.183g LiAC2H
2O, 14.853g Mn (AC)
24H
2O, 6.971gNH
4H
2PO
4(mol ratio of lithium, manganese, phosphorus is 1:1:1); 2.763g citric acid (through calculating, in the citric acid quality of carbon be raw materials quality 10%) be dissolved in the water, be configured to 300mL solution; Make that ion concentration is 0.2mol/L, constantly stirring makes raw materials mix even under magnetic agitation;
(2) precursor powder preparation: with the mixed solution of preparation, at 220 ℃ of baking temperatures, nozzle diameter 1mm, feed rate 400mL/h, atomizing pressure 0.3MPa carries out spray drying, obtains precursor powder.
(3) heat treatment: get a certain amount of precursor powder and be placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volumn concentration be 10%) adopt down the mode of temperature programming; At first the speed with 2 ℃/min is warming up to 400 ℃ of maintenance 2h with mixture; And then be heated to 600 ℃ with 5 ℃/min speed and keep 12h; Naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats;
Lithium manganese phosphate so that present embodiment prepares is tested and electrochemical property test through physical property; Synthetic ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon is spherical olivine structural, and granular size is 5 ~ 6 μ m, and itself and metal lithium sheet are done negative pole and electrode is assembled into simulated battery; Test with the 0.2C rate charge-discharge; When charging/discharging voltage was 2.0-4.5V, first discharge specific capacity was 54.1mAh/g, and 0.1C multiplying power maximum discharge capacity reaches 61.3mAh/g; Enclosed pasture efficient is 70.9% first, and 0.2C circulation 30 circle back capability retentions are 93.5%.
Embodiment 3
(1) precursor solution preparation: with 6.183g LiAC2H
2O, 14.853g Mn (AC)
24H
2O, 6.971gNH
4H
2PO
4(mol ratio of lithium, manganese, phosphorus is 1:1:1); 2.763g citric acid (through calculating, in the citric acid quality of carbon be raw materials quality 10%) be dissolved in the water, be configured to 300mL solution; Make that ion concentration is 0.2mol/L, constantly stirring makes raw materials mix even under magnetic agitation;
(2) precursor powder preparation: with the mixed solution of preparation, at 220 ℃ of baking temperatures, nozzle diameter 2mm, feed rate 400mL/h, atomizing pressure 0.3MPa carries out spray drying, obtains precursor powder;
(3) heat treatment: get a certain amount of precursor powder and be placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming; At first the speed with 2 ℃/min is warming up to 400 ℃ of maintenance 2h with mixture; And then be heated to 600 ℃ with 5 ℃/min speed and keep 3h; Naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats;
Lithium manganese phosphate so that present embodiment prepares is tested and electrochemical property test through physical property; Synthetic lithium ion battery anode material manganese lithium phosphate/carbon is spherical olivine structural, and granular size is 6 ~ 7 μ m, and itself and metal lithium sheet are done negative pole and electrode is assembled into simulated battery; Test with the 0.2C rate charge-discharge; When charging/discharging voltage was 2.0-4.5V, discharge capacity was 83.7mAh/g first, and 0.1C multiplying power maximum discharge capacity reaches 109.8mAh/g; Enclosed pasture efficient is 77.6% first, and 0.2C circulation 30 circle back capability retentions are 95.3%.
Embodiment 4
(1) precursor solution preparation: with 6.183g LiAC2H
2O, 14.853g Mn (AC)
24H
2O, 6.971gNH
4H
2PO
4(mol ratio of lithium, manganese, phosphorus is 1:1:1); 1.658g citric acid (through calculating, in the citric acid quality of carbon be raw materials quality 6%) be dissolved in the water, be configured to 300mL solution; Make that ion concentration is 0.2mol/L, constantly stirring makes raw materials mix even under magnetic agitation;
(2) precursor powder preparation: with the mixed solution of preparation, at 220 ℃ of baking temperatures, nozzle diameter 2mm, feed rate 400mL/h, atomizing pressure 0.3MPa carries out spray drying, obtains precursor powder;
(3) heat treatment: get a certain amount of precursor powder and be placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming; At first the speed with 2 ℃/min is warming up to 400 ℃ of maintenance 2h with mixture; And then be heated to 600 ℃ with 5 ℃/min speed and keep 3h; Naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
Lithium manganese phosphate so that present embodiment prepares is tested and electrochemical property test through physical property.Synthetic lithium ion battery anode material manganese lithium phosphate/carbon positive electrode is spherical olivine structural, and granular size is 4 ~ 5 μ m, and itself and metal lithium sheet are done negative pole and electrode is assembled into simulated battery; Test with the 0.2C rate charge-discharge; When charging/discharging voltage was 2.0-4.5V, discharge capacity was 79.5mAh/g first, and 0.1C multiplying power maximum discharge capacity reaches 96.2mAh/g; Enclosed pasture efficient is 74.7% first, and 0.2C circulation 30 circle back capability retentions are 92.7%.
(1) precursor solution preparation: with 4.221g LiNO
3, 21.474g Mn (NO
3)
2, 6.9176g H
3PO
4(mol ratio of lithium, manganese, phosphorus is 1:1:1); 2.763g citric acid (through calculating, in the citric acid quality of carbon be raw materials quality 10%) be dissolved in the ethanol, be configured to 300mL solution; Make that ion concentration is 0.2mol/L, constantly stirring makes raw materials mix even under magnetic agitation;
(2) precursor powder preparation: with the mixed solution of preparation, at 220 ℃ of baking temperatures, nozzle diameter 0.5mm, feed rate 400mL/h, atomizing pressure 0.3MPa carries out spray drying, obtains precursor powder;
(3) heat treatment: get a certain amount of precursor powder and be placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming; At first the speed with 2 ℃/min is warming up to 400 ℃ of maintenance 2h with mixture; And then be heated to 600 ℃ with 5 ℃/min speed and keep 12h; Naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
Lithium manganese phosphate so that present embodiment prepares is tested and electrochemical property test through physical property.Synthetic lithium ion battery anode material manganese lithium phosphate/carbon positive electrode is spherical olivine structural, and granular size is 0.6 ~ 1 μ m, and itself and metal lithium sheet are done negative pole and electrode is assembled into simulated battery; Test with the 0.2C rate charge-discharge; When charging/discharging voltage was 2.0-4.5V, discharge capacity was 60.8mAh/g first, and 0.1C multiplying power maximum discharge capacity reaches 85.4mAh/g; Enclosed pasture efficient is 72% first, and 0.2C circulation 30 circle back capability retentions are 86.7%.
Embodiment 6
(1) precursor solution preparation: with 4.221g LiNO
3, 14.853g Mn (AC)
24H
2O, 6.971gNH
4H
2PO
4(mol ratio of lithium, manganese, phosphorus is 1:1:1); 2.763g citric acid (through calculating, in the citric acid quality of carbon be raw materials quality 10%) be dissolved in the acetone, be configured to 300mL solution; Make that ion concentration is 0.2mol/L, constantly stirring makes raw materials mix even under magnetic agitation;
(2) precursor powder preparation: with the mixed solution of preparation, at 220 ℃ of baking temperatures, nozzle diameter 1.5mm, feed rate 400mL/h, atomizing pressure 0.3MPa carries out spray drying, obtains precursor powder;
(3) heat treatment: get a certain amount of precursor powder and be placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming; At first the speed with 2 ℃/min is warming up to 400 ℃ of maintenance 2h with mixture; And then be heated to 600 ℃ with 5 ℃/min speed and keep 12h; Naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
Lithium manganese phosphate so that present embodiment prepares is tested and electrochemical property test through physical property.Synthetic lithium ion battery anode material manganese lithium phosphate/carbon positive electrode is spherical olivine structural, and granular size is 1 ~ 3 μ m, and itself and metal lithium sheet are done negative pole and electrode is assembled into simulated battery; Test with the 0.2C rate charge-discharge; When charging/discharging voltage was 2.0-4.5V, discharge capacity was 71.7mAh/g first, and 0.1C multiplying power maximum discharge capacity reaches 92.1mAh/g; Enclosed pasture efficient is 74.3% first, and 0.2C circulation 30 circle back capability retentions are 88.7%.
Embodiment 7
(1) precursor solution preparation: with 6.183g LiAC2H
2O, 14.853g Mn (AC)
24H
2O, 6.971gNH
4H
2PO
4(mol ratio of lithium, manganese, phosphorus is 1:1:1); 1.45225g polyvinylpyrrolidone is (through calculating; In the citric acid quality of carbon be raw materials quality 10%) be dissolved in the ethanol water; Be configured to 300mL solution, make that ion concentration is 0.2mol/L, constantly stirring makes raw materials mix even under magnetic agitation;
(2) precursor powder preparation: with the mixed solution of preparation, at 220 ℃ of baking temperatures, nozzle diameter 2mm, feed rate 400mL/h, atomizing pressure 0.3MPa carries out spray drying, obtains precursor powder;
(3) heat treatment: get a certain amount of precursor powder and be placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming; At first the speed with 2 ℃/min is warming up to 400 ℃ of maintenance 2h with mixture; And then be heated to 600 ℃ with 5 ℃/min speed and keep 12h; Naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
Lithium manganese phosphate so that present embodiment prepares is tested and electrochemical property test through physical property.Synthetic lithium ion battery anode material manganese lithium phosphate/carbon positive electrode is spherical olivine structural, and granular size is 5 ~ 7 μ m, and itself and metal lithium sheet are done negative pole and electrode is assembled into simulated battery; Test with the 0.2C rate charge-discharge; When charging/discharging voltage was 2.0-4.5V, discharge capacity was 65.7mAh/g first, and 0.1C multiplying power maximum discharge capacity reaches 88.7mAh/g; Enclosed pasture efficient is 74.3% first, and 0.2C circulation 30 circle back capability retentions are 91.6%.
Embodiment 8
(1) precursor solution preparation: with 6.183g LiAC2H
2O, 14.853g Mn (AC)
24H
2O, 6.971gNH
4H
2PO
4(mol ratio of lithium, manganese, phosphorus is 1:1:1); 2.763g citric acid (through calculating, in the citric acid quality of carbon be raw materials quality 10%) be dissolved in the water, be configured to 300mL solution; Make that ion concentration is 0.2mol/L, constantly stirring makes raw materials mix even under magnetic agitation;
(2) precursor powder preparation: with the mixed solution of preparation, at 250 ℃ of baking temperatures, nozzle diameter 2mm, feed rate 400mL/h, atomizing pressure 0.3MPa carries out spray drying, obtains precursor powder;
(3) heat treatment: get a certain amount of precursor powder and be placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming; At first the speed with 2 ℃/min is warming up to 400 ℃ of maintenance 2h with mixture; And then be heated to 600 ℃ with 5 ℃/min speed and keep 12h; Naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
Lithium manganese phosphate so that present embodiment prepares is tested and electrochemical property test through physical property.Synthetic lithium ion battery anode material manganese lithium phosphate/carbon positive electrode is spherical olivine structural, and granular size is 4 ~ 6 μ m, and itself and metal lithium sheet are done negative pole and electrode is assembled into simulated battery; Test with the 0.2C rate charge-discharge; When charging/discharging voltage was 2.0-4.5V, discharge capacity was 60.4mAh/g first, and 0.1C multiplying power maximum discharge capacity reaches 78.7mAh/g; Enclosed pasture efficient is 74.3% first, and 0.2C circulation 30 circle back capability retentions are 90.7%.
Embodiment 9
(1) precursor solution preparation: with 6.183g LiAC2H
2O, 14.853g Mn (AC)
24H
2O, 6.971gNH
4H
2PO
4(mol ratio of lithium, manganese, phosphorus is 1:1:1); 2.763g citric acid (through calculating, in the citric acid quality of carbon be raw materials quality 10%) be dissolved in the water, be configured to 300mL solution; Make that ion concentration is 0.2mol/L, constantly stirring makes raw materials mix even under magnetic agitation;
(2) precursor powder preparation: with the mixed solution of preparation, at 270 ℃ of baking temperatures, nozzle diameter 2mm, feed rate 400mL/h, atomizing pressure 0.3MPa carries out spray drying, obtains precursor powder;
(3) heat treatment: get a certain amount of precursor powder and be placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming; At first the speed with 2 ℃/min is warming up to 400 ℃ of maintenance 2h with mixture; And then be heated to 600 ℃ with 5 ℃/min speed and keep 12h; Naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
Lithium manganese phosphate so that present embodiment prepares is tested and electrochemical property test through physical property.Synthetic lithium ion battery anode material manganese lithium phosphate/carbon positive electrode is spherical olivine structural, and granular size is 5 ~ 7 μ m, and itself and metal lithium sheet are done negative pole and electrode is assembled into simulated battery; Test with the 0.2C rate charge-discharge; When charging/discharging voltage was 2.0-4.5V, discharge capacity was 60mAh/g first, and 0.1C multiplying power maximum discharge capacity reaches 78.7mAh/g; Enclosed pasture efficient is 73.6% first, and 0.2C circulation 30 circle back capability retentions are 94.7%.
(1) precursor solution preparation: with 6.183g LiAC2H
2O, 14.853g Mn (AC)
24H
2O, 6.971gNH
4H
2PO
4(mol ratio of lithium, manganese, phosphorus is 1:1:1); 2.763g citric acid (through calculating, in the citric acid quality of carbon be raw materials quality 10%) be dissolved in the water, be configured to 300mL solution; Make that ion concentration is 0.2mol/L, constantly stirring makes raw materials mix even under magnetic agitation;
(2) precursor powder preparation: with the mixed solution of preparation, at 220 ℃ of baking temperatures, nozzle diameter 2mm, feed rate 300mL/h, atomizing pressure 0.3MPa carries out spray drying, obtains precursor powder;
(3) heat treatment: get a certain amount of precursor powder and be placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming; At first the speed with 2 ℃/min is warming up to 400 ℃ of maintenance 2h with mixture; And then be heated to 600 ℃ with 5 ℃/min speed and keep 12h; Naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
Lithium manganese phosphate so that present embodiment prepares is tested and electrochemical property test through physical property.Synthetic lithium ion battery anode material manganese lithium phosphate/carbon positive electrode is spherical olivine structural, and granular size is 4 ~ 6 μ m, and itself and metal lithium sheet are done negative pole and electrode is assembled into simulated battery; Test with the 0.2C rate charge-discharge; When charging/discharging voltage was 2.0-4.5V, discharge capacity was 71.3mAh/g first, and 0.1C multiplying power maximum discharge capacity reaches 95.7mAh/g; Enclosed pasture efficient is 74.1% first, and 0.2C circulation 30 circle back capability retentions are 93.8%.
Embodiment 11
(1) precursor solution preparation: with 6.183g LiAC2H
2O, 14.853g Mn (AC)
24H
2O, 6.971gNH
4H
2PO
4(mol ratio of lithium, manganese, phosphorus is 1:1:1); 2.763g citric acid (through calculating, in the citric acid quality of carbon be raw materials quality 10%) be dissolved in the water, be configured to 300mL solution; Make that ion concentration is 0.2mol/L, constantly stirring makes raw materials mix even under magnetic agitation;
(2) precursor powder preparation: with the mixed solution of preparation, at 220 ℃ of baking temperatures, nozzle diameter 2mm, feed rate 500mL/h, atomizing pressure 0.4MPa carries out spray drying, obtains precursor powder;
(3) heat treatment: get a certain amount of precursor powder and be placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming; At first the speed with 2 ℃/min is warming up to 400 ℃ of maintenance 2h with mixture; And then be heated to 600 ℃ with 5 ℃/min speed and keep 12h; Naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
Lithium manganese phosphate so that present embodiment prepares is tested and electrochemical property test through physical property.Synthetic lithium ion battery anode material manganese lithium phosphate/carbon positive electrode is spherical olivine structural, and granular size is 3 ~ 5 μ m, and itself and metal lithium sheet are done negative pole and electrode is assembled into simulated battery; Test with the 0.2C rate charge-discharge; When charging/discharging voltage was 2.0-4.5V, discharge capacity was 76.4mAh/g first, and 0.1C multiplying power maximum discharge capacity reaches 104.2mAh/g; Enclosed pasture efficient is 72.9% first, and 0.2C circulation 30 circle back capability retentions are 94.1%.
Embodiment 12
(1) precursor solution preparation: with 6.183g LiAC2H
2O, 14.853g Mn (AC)
24H
2O, 6.971gNH
4H
2PO
4(mol ratio of lithium, manganese, phosphorus is 1:1:1); 2.763g citric acid (through calculating, in the citric acid quality of carbon be raw materials quality 10%) be dissolved in the water, be configured to 300mL solution; Make that ion concentration is 0.2mol/L, constantly stirring makes raw materials mix even under magnetic agitation;
(2) precursor powder preparation: with the mixed solution of preparation, at 220 ℃ of baking temperatures, nozzle diameter 2mm, feed rate 400mL/h, atomizing pressure 0.2MPa carries out spray drying, obtains precursor powder;
(3) heat treatment: get a certain amount of precursor powder and be placed in the ceramic Noah's ark, at N
2Adopt the mode of temperature programming down; At first the speed with 2 ℃/min is warming up to 400 ℃ of maintenance 2h with mixture; And then be heated to 600 ℃ with 5 ℃/min speed and keep 12h; Naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed nitrogen gas, obtain the lithium manganese phosphate that carbon coats.
Lithium manganese phosphate so that present embodiment prepares is tested and electrochemical property test through physical property.Synthetic lithium ion battery anode material manganese lithium phosphate/carbon positive electrode is spherical olivine structural, and granular size is 3 ~ 5 μ m, and itself and metal lithium sheet are done negative pole and electrode is assembled into simulated battery; Test with the 0.2C rate charge-discharge; When charging/discharging voltage was 2.0-4.5V, discharge capacity was 72.5mAh/g first, and 0.1C multiplying power maximum discharge capacity reaches 101.4mAh/g; Enclosed pasture efficient is 73.2% first, and 0.2C circulation 30 circle back capability retentions are 93.7%.
Embodiment 13
(1) precursor solution preparation: with 6.183g LiAC2H
2O, 14.853g Mn (AC)
24H
2O, 6.971gNH
4H
2PO
4(mol ratio of lithium, manganese, phosphorus is 1:1:1); 2.763g citric acid (through calculating, in the citric acid quality of carbon be raw materials quality 10%) be dissolved in the water, be configured to 300mL solution; Make that ion concentration is 0.2mol/L, constantly stirring makes raw materials mix even under magnetic agitation;
(2) precursor powder preparation: with the mixed solution of preparation, at 220 ℃ of baking temperatures, nozzle diameter 2mm, feed rate 400mL/h, atomizing pressure 0.3MPa carries out spray drying, obtains precursor powder;
(3) heat treatment: get a certain amount of precursor powder and be placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming; At first the speed with 2 ℃/min is warming up to 400 ℃ of maintenance 5h with mixture; And then be heated to 600 ℃ with 5 ℃/min speed and keep 12h; Naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
Lithium manganese phosphate so that present embodiment prepares is tested and electrochemical property test through physical property.Synthetic lithium ion battery anode material manganese lithium phosphate/carbon positive electrode is spherical olivine structural, and granular size is 4 ~ 8 μ m, and itself and metal lithium sheet are done negative pole and electrode is assembled into simulated battery; Test with the 0.2C rate charge-discharge; When charging/discharging voltage was 2.0-4.5V, discharge capacity was 69.7mAh/g first, and 0.1C multiplying power maximum discharge capacity reaches 96.3mAh/g; Enclosed pasture efficient is 75.1% first, and 0.2C circulation 30 circle back capability retentions are 92.7%.
Embodiment 14
(1) precursor solution preparation: with 6.183g LiAC2H
2O, 14.853g Mn (AC)
24H
2O, 6.971gNH
4H
2PO
4(mol ratio of lithium, manganese, phosphorus is 1:1:1); 2.763g citric acid (through calculating, in the citric acid quality of carbon be raw materials quality 10%) be dissolved in the water, be configured to 300mL solution; Make that ion concentration is 0.2mol/L, constantly stirring makes raw materials mix even under magnetic agitation;
(2) precursor powder preparation: with the mixed solution of preparation, at 220 ℃ of baking temperatures, nozzle diameter 2mm, feed rate 400mL/h, atomizing pressure 0.3MPa carries out spray drying, obtains precursor powder;
(3) heat treatment: get a certain amount of precursor powder and be placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming; At first the speed with 8 ℃/min is warming up to 400 ℃ of maintenance 2h with mixture; And then be heated to 600 ℃ with 5 ℃/min speed and keep 12h; Naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
Lithium manganese phosphate so that present embodiment prepares is tested and electrochemical property test through physical property.Synthetic lithium ion battery anode material manganese lithium phosphate/carbon positive electrode is spherical olivine structural, and granular size is 3 ~ 6 μ m, and itself and metal lithium sheet are done negative pole and electrode is assembled into simulated battery; Test with the 0.2C rate charge-discharge; When charging/discharging voltage was 2.0-4.5V, discharge capacity was 76.8mAh/g first, and 0.1C multiplying power maximum discharge capacity reaches 106.4mAh/g; Enclosed pasture efficient is 72.8% first, and 0.2C circulation 30 circle back capability retentions are 93.3%.
(1) precursor solution preparation: with 6.183g LiAC2H
2O, 14.853g Mn (AC)
24H
2O, 6.971gNH
4H
2PO
4(mol ratio of lithium, manganese, phosphorus is 1:1:1); 2.763g citric acid (through calculating, in the citric acid quality of carbon be raw materials quality 10%) be dissolved in the water, be configured to 300mL solution; Make that ion concentration is 0.2mol/L, constantly stirring makes raw materials mix even under magnetic agitation;
(2) precursor powder preparation: with the mixed solution of preparation, at 220 ℃ of baking temperatures, nozzle diameter 2mm, feed rate 400mL/h, atomizing pressure 0.3MPa carries out spray drying, obtains precursor powder;
(3) heat treatment: get a certain amount of precursor powder and be placed in the ceramic Noah's ark, at Ar-H
2(H wherein
2Volume fraction be 10%) adopt down the mode of temperature programming; At first the speed with 2 ℃/min is warming up to 400 ℃ of maintenance 2h with mixture; And then be heated to 600 ℃ with 8 ℃/min speed and keep 12h; Naturally cool to room temperature in stove, in this process, continue in the tube furnace to feed argon hydrogen, obtain the lithium manganese phosphate that carbon coats.
Lithium manganese phosphate so that present embodiment prepares is tested and electrochemical property test through physical property.Synthetic lithium ion battery anode material manganese lithium phosphate/carbon positive electrode is spherical olivine structural, and granular size is 3 ~ 6 μ m, and itself and metal lithium sheet are done negative pole and electrode is assembled into simulated battery; Test with the 0.2C rate charge-discharge; When charging/discharging voltage was 2.0-4.5V, discharge capacity was 78.3mAh/g first, and 0.1C multiplying power maximum discharge capacity reaches 108.6mAh/g; Enclosed pasture efficient is 72.3% first, and 0.2C circulation 30 circle back capability retentions are 94.6%.
The present invention will be described more than to enumerate specific embodiment.It is pointed out that above embodiment only is used for the present invention is described further, do not represent protection scope of the present invention, nonessential modification and adjustment that other people prompting according to the present invention is made still belong to protection scope of the present invention.
Claims (8)
1. the preparation method of a ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon is characterized in that containing following steps: after getting lithium source, phosphorus source, manganese source and carbon source mixing, be scattered in the liquid medium, obtain finely dispersed precursor solution through stirring; Temperature when regulating spray drying is 220 ~ 270 ℃, and feed rate is 300 ~ 500mL/h, and nozzle diameter is 0.5 ~ 2mm; Atomizing pressure is 0.2 ~ 0.4MPa; Precursor solution is carried out spray drying, obtain precursor powder, precursor powder is heat-treated; Heat treatment is that 1 ~ 10 ℃/min is warming up to 400 ℃ ~ 600 ℃ precursor powder carried out calcination process 3 ~ 20h with heating rate under the protective gas effect, obtains ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon through being cooled to room temperature.
2. the preparation method of ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon according to claim 1 is characterized in that: the mol ratio of lithium, phosphorus, manganese is 1 ︰, 1 ︰ 1 in lithium source, phosphorus source and the manganese source; The consumption of carbon source accounts for 6 ~ 15% of lithium source, phosphorus source and manganese source total weight.
3. the preparation method of ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon according to claim 2 is characterized in that: the quality percentage composition of carbon is 1 ~ 10% in the carbon source.
4. according to the preparation method of claim 1,2 or 3 described ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon, it is characterized in that: said lithium source is one or more in lithium acetate, lithium chloride, lithium sulfate, lithium nitrate and the lithium dihydrogen phosphate; Said phosphorus source is one or more in phosphoric acid, ammonium dihydrogen phosphate and the lithium dihydrogen phosphate; Said manganese source is one or more in manganese acetate, manganese nitrate, manganese sulfate and the manganese chloride; Said carbon source is one or more in phenolic resins, sucrose, citric acid, glucose, ascorbic acid, cellulose, polyvinylpyrrolidone and the polyethylene glycol.
5. the preparation method of ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon according to claim 1 is characterized in that: said liquid medium is water, ethanol, acetone, water-ethanol solution, ethylene glycol or polyethylene glycol.
6. the preparation method of ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon according to claim 1; It is characterized in that: said protective gas is mist or the mist of nitrogen and argon gas of mist, argon gas and the hydrogen of nitrogen, nitrogen and hydrogen, and wherein the volumn concentration of hydrogen is 2 ~ 10% in the mist of argon gas and hydrogen.
7. the preparation method of ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon according to claim 1; It is characterized in that: heat treatment is that 1 ~ 10 ℃/min is warming up to 400 ℃ earlier precursor powder carried out calcination process 2 ~ 5h with heating rate under the protective gas effect, and continuing with heating rate is that 1 ~ 10 ℃/min is warming up to 600 ℃ precursor powder carried out calcination process 1 ~ 15h again.
8. the preparation method of ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon according to claim 1; It is characterized in that: obtain the primary particle of ball-shaped lithium-ion battery anode material lithium manganese phosphate/carbon for being reunited and formed by second particle through being cooled to room temperature, the size of this primary particle is 3 ~ 10 μ m.
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| CN103000893A (en) * | 2012-12-20 | 2013-03-27 | 中国东方电气集团有限公司 | Method for preparing lithium manganese phosphate positive material of lithium battery by spray pyrolysis |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007048612A (en) * | 2005-08-10 | 2007-02-22 | Saga Univ | Active material for lithium cell |
| CN101320809A (en) * | 2008-07-17 | 2008-12-10 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery anode material manganese lithium phosphate and preparation method thereof |
| CN102610816A (en) * | 2012-03-12 | 2012-07-25 | 中国科学院过程工程研究所 | Fiber-ball-shaped lithium manganese phosphate anode material of lithium ion battery and preparation method of fiber-ball-shaped lithium manganese phosphate anode material |
-
2012
- 2012-07-30 CN CN2012102659832A patent/CN102790213A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007048612A (en) * | 2005-08-10 | 2007-02-22 | Saga Univ | Active material for lithium cell |
| CN101320809A (en) * | 2008-07-17 | 2008-12-10 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery anode material manganese lithium phosphate and preparation method thereof |
| CN102610816A (en) * | 2012-03-12 | 2012-07-25 | 中国科学院过程工程研究所 | Fiber-ball-shaped lithium manganese phosphate anode material of lithium ion battery and preparation method of fiber-ball-shaped lithium manganese phosphate anode material |
Cited By (16)
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| CN103000888B (en) * | 2012-11-28 | 2015-10-14 | 上海交通大学 | Lithium ion battery composite cathode material LiMnPO4-Li3V2 (PO4) 3/C and preparation method thereof |
| CN103000893A (en) * | 2012-12-20 | 2013-03-27 | 中国东方电气集团有限公司 | Method for preparing lithium manganese phosphate positive material of lithium battery by spray pyrolysis |
| CN103000893B (en) * | 2012-12-20 | 2016-02-17 | 中国东方电气集团有限公司 | A kind of spray pyrolysis preparation method of lithium battery manganese-lithium phosphate anode material |
| CN103066283A (en) * | 2013-01-15 | 2013-04-24 | 上海大学 | Method for preparing lithium manganese phosphate material with three-dimensional ordered macroporous structure |
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| CN113809319A (en) * | 2021-08-03 | 2021-12-17 | 广东邦普循环科技有限公司 | High-performance lithium nickel cobalt manganese oxide positive electrode material for power battery and preparation method of high-performance lithium nickel cobalt manganese oxide positive electrode material |
| CN113809319B (en) * | 2021-08-03 | 2022-11-15 | 广东邦普循环科技有限公司 | High-performance lithium nickel cobalt manganese oxide positive electrode material for power battery and preparation method of high-performance lithium nickel cobalt manganese oxide positive electrode material |
| CN115295781A (en) * | 2022-08-10 | 2022-11-04 | 广东比沃新能源有限公司 | Manganese-based positive electrode material and application thereof in lithium battery |
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