CN102427131A - Preparation method for metal magnesium-doped lithium manganese phosphate/carbon cathode material of lithium ion battery - Google Patents
Preparation method for metal magnesium-doped lithium manganese phosphate/carbon cathode material of lithium ion battery Download PDFInfo
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- CN102427131A CN102427131A CN2011102673549A CN201110267354A CN102427131A CN 102427131 A CN102427131 A CN 102427131A CN 2011102673549 A CN2011102673549 A CN 2011102673549A CN 201110267354 A CN201110267354 A CN 201110267354A CN 102427131 A CN102427131 A CN 102427131A
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Abstract
The invention discloses a preparation method for a metal magnesium-doped lithium manganese phosphate/carbon cathode material of a lithium ion battery. The preparation method comprises the following steps of: (1) preparing a precursor, namely ball-milling and uniformly mixing a lithium source compound, a phosphorous source compound, a manganese source compound, a magnesium source compound and a carbon source compound; (2) ball-milling and crushing the precursor, namely drying a mixture obtained by the step (1), and ball-milling the mixture into particles; and (3) performing roasting treatment, namely calcining the mixture for 1 to 12h in the inert atmosphere of 500 to 800 DEG C to obtain carbon-coated magnesium-doped lithium manganese phosphate particles. Carbon is coated and magnesium is doped, so that the electron conductivity of lithium manganese phosphate can be improved, the particles can be prevented from being agglomerated and the structure of the lithium manganese phosphate can be stabilized; and the particle sizes of the particles are remarkably decreased and can be 300 to 500nm, and the particles are almost spherical, rhombic or blocky. A lithium ion secondary battery prepared from the material has the discharge voltage of about 4V, high charge and discharge capacity and high cyclical stability.
Description
Technical field
The present invention relates to a kind of ion battery positive pole material manganese lithium phosphate magnesium lithium/carbon preparation method, be meant especially and utilize lithium ion battery anode material manganese lithium phosphate/carbon that the synthetic magnesium of a step solid phase method mixes, carbon coats, belong to energy new material technology field.
Background technology
At present, anode material for lithium-ion batteries mainly contains several kinds of lithium and cobalt oxides, lithium manganese oxide, ternary material and transition metal phosphates.Lithium and cobalt oxides obtains commercial the use as cell positive material the earliest, yet cobalt is as strategic resource, and shortage of resources, cost is high, toxicity is higher, and has poor heat stability, the relatively poor shortcoming of fail safe, has limited its further development.Lithium manganese oxide anode material aboundresources, cost are low, but its electrochemistry capacitance is lower, and its application of high-temperature behavior official post is restricted.
In recent years, li-contained phosphate LiMPO
4(M=Mn, Fe, Co, Ni etc.) receive extensive concern, LiMPO as the basic research of lithium ion battery material
4(M=Mn, Fe, Co, Ni) serial electrode material belongs to polyanion type compound, has olivine-type structure, and is different fully with the structure of ordinary oxide electrode material, thereby, have unique chemical property.Wherein, LiFePO
4Be to study one of focus at present, its theoretical capacity is about 170mAh/g, but it is with respect to Li
+The electrode potential of/Li is merely 3.4V.LiCoPO
4And LiNiPO
4Voltage platform respectively 4.8 and 5.1V, exceeded the scope that existing lithium-ion battery electrolytes can bear, the researcher carries out Theoretical Calculation and finds LiMnPO in these materials
4With respect to Li
+The electrode potential of/Li is 4.1V, is positioned at the stable electrochemical window of existing electrolyte system, and this material has the advantage of potential high-energy-density, and this material has advantages such as cost is low, environmentally friendly.Yet employings such as YAMADA first principle calculates electron energy level, and electronics is at LiFePO
4The middle energy gap that transition takes place is 0.3eV, and characteristic of semiconductor is arranged, and LiMnPO
4Be 2eV, the electron conduction extreme difference belongs to insulator, the synthetic LiMnPO that can reversiblely discharge and recharge
4Unusual difficulty will be if after the conductance of lithium manganese phosphate material brought up to 90 ~ 100S/cm, this material will be more promising than LiFePO4.Show: (1) output voltage is high, can reach 4.1 ~ 4.5V, and energy density is higher more than 30% than LiFePO4; (2) stable in the air, can simplify synthetic working condition; (3) energy density is moderate, and theoretical specific capacity and LiFePO4 are close; (4) manganese salt aboundresources, low price; (5) Mn
3+Oxidizability very a little less than, to electrolyte safety.
For improving LiMnPO
4The chemical property of material, relatively effective method is to obtain nanoscale LiMnPO
4Particulate.Synthesized nanoscale LiMnPO like ThierryDrezen in 2007 with sol-gel process
4, reversible capacity reaches 156mAh/g, 134mAh/g respectively at 0.01C, 0.1C.DeyuWang in 2009 is through hydro thermal method and add the LiMnPO of polyalcohol synthesized high-performance, nanostructure
4, specific capacity is respectively 145mAh/g, 141mAh/g, 113mAh/g at 0.05C, 0.1C, 1C.Nanoscale LiMnPO
4Better electrochemical performance can shorten the evolving path of lithium ion owing to little particle size; Increase the effective diffusion cofficient of lithium ion; But corresponding solwution method building-up process is complicated, generated time is long, complex operation, thereby is difficult to be applied in the actual commercial production.
At present, synthetic the most widely used method of lithium manganese phosphate is a high-temperature solid phase reaction method, also is best suited for realizing industrialized production method.Wang Zhixing etc. adopt Li
2CO
3, MnCO
3, NH
4H
2PO
4Be raw material, add an amount of carbon black and mix that first ball milling 36h, 300 ℃ of pre-burning 3h take out intermediate product and continue ball milling 24h, calcine 24h for 600 ℃, obtain the olivine structural LiMnPO of pure phase
4, discharge capacity is 95mAh/g.This synthetic method uses lithium salts, manganese salt and phosphate to be raw material, through pre-burning, adds carbon reduction and hydrogen reducing roasting, and operating process is complicated, and has sintetics purity problem of lower.
Summary of the invention
The objective of the invention is to improve the deficiency of existing lithium manganese phosphate charge-discharge performance, and a kind of preparation method of new ion battery positive pole material manganese lithium phosphate magnesium lithium is provided.
For solving the technical problem of the magnesium-doped ion lithium manganese phosphate of preparation; The present invention provides a kind of mode of simple ball milling bag carbon calcining of utilizing to prepare ion battery positive pole material manganese lithium phosphate magnesium lithium/carbon; Purpose provides a kind of ion battery positive pole material manganese lithium phosphate magnesium lithium preparation method, thereby carries highly magnesium-doped lithium manganese phosphate positive electrode chemical property.
The present invention adopts following technical scheme to realize its goal of the invention: said ion battery positive pole material manganese lithium phosphate magnesium lithium/carbon has the lithium manganese phosphate matrix; There is part manganese position to be replaced in the matrix by magnesium ion; Matrix is coated with the material with carbon element coating layer, and prepared manganese phosphate magnesium lithium has almost spherical, rhombus or block microscopic feature.
The granularity of ion battery positive pole material manganese lithium phosphate magnesium lithium of the present invention is 300 ~ 500nm.
A kind of preparation method of lithium ion cell positive manganese phosphate magnesium lithium may further comprise the steps:
1) presoma preparation: with a certain amount of Li source compound, P source compound, magnesium source compound and manganese source compound and carbon-source cpd, add liquid medium, ball milling appropriate time under certain rotating speed extremely with said raw material and said carbon-source cpd submergence;
2) the mixture dry run behind the ball milling: after the mixed material ball milling is accomplished, the mixture taking-up that obtains is placed on evaporating dish, dry in 60 ~ 100 ℃ of vacuum drying chambers;
3) the mixture ball milling that ball mill grinding presoma: with step 2) obtains becomes particulate, and ball milling speed is 300 ~ 500r/min, and the time is 2 ~ 12h;
4) calcination process: the above-mentioned mixture particulate that obtains is transferred in the porcelain boat, and under 500 ~ 800 ℃ of protective atmospheres, calcining 1 ~ 12h naturally cools to room temperature, obtains carbon and coats magnesium doping phosphoric acid manganese lithium particulate;
5) sonicated: the active material after will calcining carries out ultrasonic cleaning, and the time is 15 ~ 45min.
Step 1) of the present invention adopts the wet ball grinding mode with lithium source, phosphorus source, magnesium source and manganese source compound, is the mixed of 1.0-1.1:1-x:x:1 by lithium, manganese, magnesium, phosphorus mol ratio.
Above-mentioned steps 1) quality of carbon is 1 ~ 12% of a raw materials quality in the said carbon-source cpd.
Above-mentioned steps 1) rotational speed of ball-mill is 200 ~ 500r/min, and the ball milling time is 2 ~ 24h.
Step 3) of the present invention adopts the mode of temperature programming to be warming up to 500～800 ℃.At first mixture is warming up between 200～400 ℃, keeps 2～6h, continue to be warming up to 500～800 ℃ then, keep 1～12h again.
Above-mentioned steps 4) programming rate of taking is controlled to be 1～10 ℃/min.
Li source compound of the present invention is preferably a kind of in lithium carbonate, lithium hydroxide, lithium acetate, lithium chloride, lithium sulfate, lithium nitrate, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate or the lithium oxalate or their mixture.
Manganese source compound of the present invention is preferably a kind of in manganese carbonate, manganese acetate, manganese dioxide, manganese dioxide or the manganous hydroxide or their mixture.
P source compound of the present invention preferably do for oneself a kind of in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus pentoxide, phosphoric acid hydrogen two lithiums or the lithium dihydrogen phosphate or their mixture.
Magnesium source compound of the present invention preferably do for oneself a kind of in magnesium nitrate, magnesium acetate, magnesia, magnesium chloride or the magnesium sulfate or their mixture.
Carbon-source cpd of the present invention preferably do for oneself a kind of of phenolic resins, carbon black, sucrose, glucose, ascorbic acid, lactose, polysaccharide, cellulose, acetylene black, polyethylene glycol, Ketjen black, polyacrylonitrile and citric acid or their mixture.
Liquid medium of the present invention is a kind of in water, ethanol, acetone, water-ethanol, ethylene glycol, the polyethylene glycol.
Protective atmosphere of the present invention is a kind of in the mist of nitrogen, nitrogen and hydrogen, argon gas and hydrogen, nitrogen and argon gas, and wherein the volume content of hydrogen is 2～10% in argon-hydrogen gaseous mixture.
The synthetic method of anode material for lithium-ion batteries provided by the present invention can reach following technique effect:
Coat the electronic conductance property of improving lithium manganese phosphate through the phase carbon source wet-milling; Adopt magnesium ion to mix and improve the ionic conductivity of lithium manganese phosphate; Then through the synthetic positive pole material phosphoric acid manganese magnesium lithium/carbon particulate of solid phase method, the manganese phosphate magnesium lithium average grain diameter that obtains is 300～500nm, the little and epigranular dispersion of particle; Carbon is even to the coating of active material, can effectively stop particle agglomeration.The manganese phosphate magnesium lithium anode material of this method preparation has the discharge voltage about 4V, and first discharge specific capacity can reach 144mAh/g under 25 ℃, 0.05C multiplying power, and has excellent cyclical stability.This preparation technology's program is simple, production cost is low, help program control, little and be suitable for suitability for industrialized production to the influence of environment.
Description of drawings
Fig. 1 is the X-ray diffracting spectrum of the manganese phosphate magnesium lithium of embodiment 1 preparation.
Fig. 2 is the sem photograph of the manganese phosphate magnesium lithium of embodiment 1 preparation.
Fig. 3 be the manganese phosphate magnesium lithium of embodiment 1 preparation under 0.05C and 0.1C multiplying power, 2.0-4.5V discharges and recharges electric curve.
Fig. 4 be the manganese phosphate magnesium lithium of embodiment 1 preparation under the 0.1C multiplying power, the capacity cycle performance curve that 2.0-4.5V discharges and recharges.
Fig. 5 be the manganese phosphate magnesium lithium of embodiment 1 preparation under the 0.05C-2C multiplying power, 2.0-4.5V charge-discharge magnification performance map.
Embodiment
Below in conjunction with embodiment the present invention is done further description so that those skilled in the art can better understand the present invention and implementing, but the embodiment that lifts not conduct to qualification of the present invention.
Embodiment 1
1) presoma preparation: with 0.3999g Li
2CO
3, 1.10352g MnCO
3, 0.08663g Mg (AC)
24H
2O and 1.162g NH
4H
2PO
4(mol ratio of lithium, manganese, magnesium, phosphorus is 1.05:0.96:0.04:1); Join in the 100ml ball grinder; Add above-mentioned phenolic resins ethanolic solution 0.785ml then (through calculating; In the phenolic resins quality of carbon be raw materials quality 6%), add ethanol at last with the raw material submergence, ball milling 12h under the 300rpm rotating speed.
2) ball mill grinding presoma: after ball milling was accomplished, the mixture that obtains is dry in 80 ℃ of air dry ovens, and the mixture that drying is good was tiled at the bottom of the ball grinder, on ball mill, with the speed ball milling 4h of 400r/min, preserved powder taking-up in the ball grinder subsequent use.
3) presoma calcining: the mixture of getting after a certain amount of said process is pulverized is 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 350 ℃ of maintenance 5h 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 carbon and coat the manganese phosphate magnesium lithium (LiMn that magnesium mixes
0.96Mg
0.04PO
4/ C).
Electrochemical property test carries out through button battery; Be used for material sample that the positive pole of the button-shaped simulated battery of electric performance test makes by embodiment, conductive agent acetylene black, binding agent PVDF ratio according to mass ratio 75:20:5; Make solvent with N-methyl pyrrolidone NMP and be applied on the Al paper tinsel after evenly, behind 110 ℃ of dry 2h, on the particulate tablet press machine 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 0.05C rate charge-discharge 5 times, carry out charge-discharge test with the 0.1C 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 45 weeks of circulating first.
The x-ray diffraction pattern of the finished-product material that embodiment 1 makes is as shown in Figure 1, and through knowing that with the comparative analysis of standard diagram card synthetic material is the higher olivine-type phase of purity, space group belongs to Pmnb.
Fig. 2 for calcining after the sem photograph of the manganese phosphate magnesium lithium that obtains, 5000 times of following stereoscan photographs are observed, the one-shot forming particle of material is a nano-scale particle; Diameter of particle is 300-400nm; Type of having spherical structure, dispersion of materials is even, does not have agglomeration basically and takes place.
Fig. 3 be manganese phosphate magnesium lithium material with the first charge-discharge curve under the 0.05C multiplying power, charging/discharging voltage is 2.0-4.5V, discharge capacity is 144mAh/g first; Enclosed pasture efficient is 81.9% first, and Fig. 4 is the cycle performance figure of manganese phosphate magnesium lithium material under the 0.1C multiplying power, and the trend of decay is arranged with circulation volume; But all in all, the material cycle performance is better, and discharge capacity is 130.7mAh/g first; Capacity behind circulation 45 circles is 123.3mAh/g, capability retention 94.3%, and institute's synthetic material is decayed bigger under the 0.05C 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.
Fig. 5 provides be material under different multiplying, discharge capacity increases with multiplying power and reduces, the 1C discharge capacity has 84.49mAh/g, the 2C discharge capacity still has 68.3mAh/g; Discharge and recharge with the 0.1C multiplying power after the 2C rate charge-discharge, capacity is 121mAh/g, can return to the capacity under the initial 0.1C multiplying power, shows that material has high rate performance preferably again.
The material electrochemical performance that is shown preparation by above-mentioned experimental data is good.
1) presoma preparation: with 0.3999g Li
2CO
3, 1.092g MnCO
3, 0.1083g Mg (AC)
2With 1.162g NH
4H
2PO
4(mol ratio of lithium, manganese, magnesium, phosphorus is 1.05:0.99:0.01:1); Add in the 100ml ball grinder; Add above-mentioned phenolic resins ethanolic solution 0.785ml then (through calculating; In the phenolic resins quality of carbon be raw materials quality 6%), add ethanol at last with the raw material submergence, ball milling 12h under the 300rpm rotating speed.
2) ball mill grinding presoma: after ball milling was accomplished, the mixture that obtains is dry in 80 ℃ of air dry ovens, and the mixture that drying is good was tiled at the bottom of the ball grinder, on ball mill, with the speed ball milling 4h of 400r/min, preserved powder taking-up in the ball grinder subsequent use.
3) presoma calcining: the mixture of getting after a certain amount of said process is pulverized is 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 350 ℃ of maintenance 5h 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 carbon and coat the manganese phosphate magnesium lithium (LiMn that magnesium mixes
0.99Mg
0.01PO
4/ C).
The LiMn for preparing with present embodiment
0.99Mg
0.01PO
4/ C is through physical property test and electrochemical property test.Synthetic material type of being is spherical, granular size 300-500nm, and itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery; Test with the 0.1C rate charge-discharge; During charging/discharging voltage 2.0-4.5V, discharge capacity is 96mAh/g first, and 0.05C multiplying power maximum discharge capacity reaches 108mAh/g; Enclosed pasture efficient is 72.4% first, and 0.1C circulation 45 circle back capability retentions are 92.7%.
Embodiment 3
1) presoma preparation: with 0.3999g Li
2CO
3, 1.03455g MnCO
3, 0.2166g Mg (AC)
24H
2O and 1.162g NH
4H
2PO
4(mol ratio of lithium, manganese, magnesium, phosphorus is 1.05:0.9:0.1:1); Add in the 100ml ball grinder; Add above-mentioned phenolic resins ethanolic solution 0.785ml then (through calculating; In the phenolic resins quality of carbon be raw materials quality 6%), add ethanol at last with the raw material submergence, ball milling 12h under the 300rpm rotating speed.
2) ball mill grinding presoma: after ball milling was accomplished, the mixture that obtains is dry in 80 ℃ of air dry ovens, and the mixture that drying is good was tiled at the bottom of the ball grinder, on ball mill, with the speed ball milling 4h of 400r/min, preserved powder taking-up in the ball grinder subsequent use.
3) presoma calcining: the mixture of getting after a certain amount of said process is pulverized is 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 350 ℃ of maintenance 5h 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 carbon and coat the manganese phosphate magnesium lithium (LiMn that magnesium mixes
0.9Mg
0.1PO
4/ C).
The LiMn for preparing with present embodiment
0.9Mg
0.1PO
4/ C is through physical property test and electrochemical property test.Synthetic material type of being is spherical, and granular size is 300-500nm, rhombus, taper or bulk; Itself and metal lithium sheet are done negative pole and electrode are assembled into simulated battery, with the test of 0.1C rate charge-discharge, when charging/discharging voltage is 2.0-4.5V; Discharge capacity is 121.3mAh/g first; 0.05C the multiplying power maximum discharge capacity reaches 138.4mAh/g, enclosed pasture efficient is 82.1% first, and 0.1C circulation 45 circle back capability retentions are 91.3%.
Visible by the foregoing description 1-3; Ion battery positive pole material manganese lithium phosphate magnesium lithium of the present invention has the discharge platform voltage about 4V; Be higher than at present the lithium iron phosphate positive material of industrialization, and prepared manganese phosphate magnesium lithium anode material has than high discharge capacity, can reach about 140mAh/g; Cycle performance is excellent simultaneously, and 45 circle capacity attenuations are less.Therefore using very advantageous aspect hybrid electric vehicle HEV, electric motor car EV and the electric tool.
Claims (12)
1. ion battery positive pole material manganese lithium phosphate magnesium lithium/carbon; It is characterized in that: said ion battery positive pole material manganese lithium phosphate magnesium lithium/carbon has the lithium manganese phosphate matrix; The manganese position is replaced by the part magnesium ion in the matrix; Matrix is coated with material with carbon element, and the manganese phosphate magnesium lithium of preparation has almost spherical, rhombus or block microscopic feature.
2. preparation method of the present invention, its characteristic mainly may further comprise the steps:
1) presoma preparation: get Li source compound, P source compound, magnesium source compound and manganese source compound; Mol ratio according to lithium, manganese, magnesium, phosphorus is the mixed of 1.0 ~ 1.1:1-x:x:1; Add carbon-source cpd; Add liquid medium again with the above-mentioned raw materials submergence, ball milling 2-24h under the 200-500r/min rotating speed, the quality of carbon is 1 ~ 12% of a raw materials quality in the carbon-source cpd;
2) the presoma ball mill grinding is handled: the mixture that step 1) is obtained carries out drying, and ball milling becomes particulate, ball milling speed 300-500r/min, time 2-12h;
3) presoma that calcination process: with step 2) obtains is put into the programming rate intensification of tube furnace with 1-10 ℃/min, and under 500-800 ℃ of inert atmosphere, calcining 1-12h is cooled to room temperature naturally, obtains carbon and coats the lithium manganese phosphate that magnesium mixes;
4) sonicated: the active material after will calcining carries out ultrasonic cleaning, and the time is 15-60min.
3. lithium ion anode material manganese phosphate magnesium lithium according to claim 1, it is characterized in that: the granularity of said ion battery positive pole material manganese lithium phosphate magnesium lithium is 300-800nm.
4. the preparation method of ion battery positive pole material manganese lithium phosphate magnesium lithium according to claim 1 is characterized in that: said Li source compound is lithium carbonate, lithium hydroxide, lithium acetate, lithium chloride, lithium sulfate, lithium nitrate, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate or lithium oxalate.
5. the preparation method of ion battery positive pole material manganese lithium phosphate magnesium lithium according to claim 1 is characterized in that: said manganese source compound is manganese carbonate, manganese acetate, manganese dioxide, manganese dioxide or manganous hydroxide.
6. the preparation method of ion battery positive pole material manganese lithium phosphate magnesium lithium according to claim 1 is characterized in that: said P source compound is phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus pentoxide, phosphoric acid hydrogen two lithiums or lithium dihydrogen phosphate.
7. the preparation method of ion battery positive pole material manganese lithium phosphate magnesium lithium according to claim 1 is characterized in that: said magnesium source compound is magnesium nitrate, magnesium acetate, magnesia, magnesium chloride or magnesium sulfate.
8. the preparation method of ion battery positive pole material manganese lithium phosphate magnesium lithium according to claim 1 is characterized in that: said carbon-source cpd is phenolic resins, carbon black, sucrose, glucose, ascorbic acid, lactose, polysaccharide, cellulose, acetylene black, polyethylene glycol, Ketjen black, polyacrylonitrile and citric acid.
9. the preparation method of ion battery positive pole material manganese lithium phosphate magnesium lithium according to claim 1 is characterized in that: described liquid medium is a kind of in water, ethanol, acetone, water-ethanol solution, ethylene glycol and the polyethylene glycol.
10. the preparation method of ion battery positive pole material manganese lithium phosphate magnesium lithium according to claim 1 is characterized in that: said protective atmosphere is the mist of nitrogen or nitrogen and hydrogen or argon gas and hydrogen or nitrogen and argon gas.
11. the preparation method of ion battery positive pole material manganese lithium phosphate magnesium lithium according to claim 1 is characterized in that: said with Li source compound, water-insoluble manganese source compound, P source compound, magnesium source compound and carbon-source cpd processing to micron or nano-scale particle employing wet ball grinding method.
12. the preparation method of ion battery positive pole material manganese lithium phosphate magnesium lithium according to claim 1; It is characterized in that: described calcination process process is under protective gas, to heat up with 1-10 ℃/min programming rate; 250-400 ℃ of preliminary treatment 2-6h; Calcine 1-12h down, naturally cool to room temperature at last for 500-800 ℃.
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| CN102931405B (en) * | 2012-11-19 | 2015-06-10 | 中国科学院宁波材料技术与工程研究所 | Lithium manganese phosphate cathode material and preparation method thereof |
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