CN103050683A - Polyphase manganese base solid solution composite cathode material and preparation method thereof - Google Patents
Polyphase manganese base solid solution composite cathode material and preparation method thereof Download PDFInfo
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- CN103050683A CN103050683A CN2012105843921A CN201210584392A CN103050683A CN 103050683 A CN103050683 A CN 103050683A CN 2012105843921 A CN2012105843921 A CN 2012105843921A CN 201210584392 A CN201210584392 A CN 201210584392A CN 103050683 A CN103050683 A CN 103050683A
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Abstract
The invention relates to a preparation method of polyphase manganese base solid solution composite cathode material, which is characterized in that manganese salt, nickel salt, cobalt salt and lithium salt are taken as raw materials, novel polyphase manganese base solid solution is prepared, and then nano highly-conductive graphene is composited on the surface of the novel polyphase manganese base solid solution, so that the polyphase manganese base solid solution composite cathode material is obtained. Compared with the prior art, the polyphase manganese base solid solution composite cathode material comprises three solid solution phases, namely, monoclinal layered Li2MnO3 with space group of C2/m and rocking chair layered LiMn0.5-xNi0.5-xCo2xO2 with space group of R-3m and three-dimensional network structure high-voltage spinel LiMn1.5-xNi0.5-xCo2xO4 with space group of Fd3m, and through introducing the LiMn1.5-xNi0.5-xCo2xO4 phase and the graphene thin layer, the intrinsic electronic conductivity and ionic conductivity of the solid solution are obviously improved, the first irreversible capacity is reduced, and the low-temperature property and rate capability are obviously improved.
Description
Technical field
The present invention relates to the anode material for lithium-ion batteries field, particularly, the present invention relates to a kind of heterogeneous manganese based solid solution composite positive pole and preparation method thereof.
Background technology
High-energy-density and high-specific-power be the future market to the inevitable demand of lithium ion battery, and the anode material for lithium-ion batteries of development high power capacity and high rate capability is key wherein.Business-like anode material for lithium-ion batteries LiCoO
2, LiMn
2O
4, LiFePO
4Deng specific discharge capacity all below 200mAh/g, its energy density is limited.And lithium-rich anode material particularly lithium-rich manganese-based anode material is because the specific capacity of superelevation and cheaper price have caused pays close attention to widely, the lithium-rich manganese-based anode material of report mainly is stratified material Li at present
2MnO
3And LiMO
2(M=Ni, Co, Mn) solid solution that forms, this solid solution specific discharge capacity up to the theoretical specific discharge capacity of 250mAh/g(more than 300mAh/g), can satisfy following electric automobile power battery to the demand of high-energy-density, be present one of the most potential anode material for lithium-ion batteries.
Although lithium-rich manganese-based solid-solution material has significant advantage, but consider from practical angle, still exist many difficult problems to need to be resolved hurrily: (1) is coulombic efficiency low (generally only 60～70%) first, the negative material demand that causes matching increases, and is difficult to realize reducing the target of battery weight and cost of manufacture; (2) the intrinsic electron conduction is not good, causes the high rate performance of material poor, is difficult to satisfy the requirement of electrokinetic cell; (3) the intrinsic ionic conductivity is poor, causes the cryogenic property of material relatively poor, and the scope of application is restricted.
CN102751483A discloses the lithium-rich manganese-based solid solution cathode material preparation method of a kind of lithium ion battery stratiform.This positive electrode adopts heat-treats method preparation with cooling processing to presoma, and its chemical formula is: xLi
2MnO
3(1-x) LiMn
0.4Ni
0.4Co
0.2O
2(x=0.1～1.0).The material of the method preparation has higher specific discharge capacity and cyclical stability preferably, but its high rate performance under large electric current is relatively poor, specific discharge capacity only is about 160mAh/g in the time of 1C(200mA/g), and the first charge-discharge coulombic efficiency is lower, and this can't satisfy the requirement of electrical equipment needs fast charging and discharging.
Based on this, the present invention proposes the heterogeneous manganese based solid solution of a kind of lithium ion battery composite positive pole and preparation method thereof.
Summary of the invention
The first coulombic efficiency that exists for manganese based solid solution material in the prior art is low, the problem of multiplying power and poor performance at low temperatures, one of purpose of the present invention has been to provide a kind of capacity and first high, the multiplying power of efficient and the good heterogeneous manganese based solid solution of the lithium ion battery composite positive pole of cryogenic property, has the spinelle LiMn that enriches three-dimensional net structure by introducing
1.5-xNi
0.5-xCo
2xO
4Mutually and the even Graphene thin layer of high conductivity, significantly improve intrinsic electronic conductivity and the ionic conductivity of solid-solution material, effectively solved an above-mentioned difficult problem.
Described heterogeneous manganese based solid solution composite positive pole comprises heterogeneous manganese based solid solution and Graphene, and wherein, described heterogeneous manganese based solid solution comprises Li
2MnO
3, LiMn
0.5-xNi
0.5-xCo
2xO
2And LiMn
1.5-xNi
0.5-xCo
2xO
4Three-phase, 0≤x＜0.5.
It is the monocline stratiform Li of C2/m that described heterogeneous manganese based solid solution has comprised space group
2MnO
3, space group is the rocking chair stratiform LiMn of R-3m
0.5-xNi
0.5-xCo
2xO
2With space group be the three-dimensional net structure spinelle LiMn of Fd3m
1.5-xNi
0.5-xCo
2xO
4Three-phase.Li
2MnO
3Have rock-steady structure and storage lithium performance, LiMn
0.5-xNi
0.5-xCo
2xO
2Has high power capacity, LiMn
1.5-xNi
0.5-xCo
2xO
4Has high rate capability.
Preferably, the general formula of described heterogeneous manganese based solid solution is aLiMn
1.5-xNi
0.5-xCo
2xO
4BLi
2MnO
3CLiMn
0.5-xNi
0.5-xCo
2xO
2, 0≤x＜0.5 wherein, a:b:c is (0 ~ 0.5): (0.1 ~ 0.7): (0.1 ~ 0.7), and 0＜a≤0.5, a+b+c=1.
Preferably, described a:b:c is (0 ~ 0.3): (0.3 ~ 0.6): (0.3 ~ 0.6), and 0＜a≤0.3, a+b+c=1, particularly preferably, described a:b:c is (0 ~ 0.2): (0.4 ~ 0.5): (0.4 ~ 0.5), and 0＜a≤0.2, b=c, a+b+c=1.
Preferably, the mass ratio that described Graphene accounts for heterogeneous manganese based solid solution is 0.05:100 ~ 20:100,0.08:100 ~ 15:100 more preferably, 0.1:100 ~ 10:100.
One of purpose of the present invention has been to provide a kind of preparation method of described heterogeneous manganese based solid solution composite positive pole.The preparation method of described heterogeneous manganese based solid solution composite positive pole prepares on the basis of spheroidization homogeneous phase presoma at drying process with atomizing, by control Li/M(M=Mn, Ni, Co) molar ratio and Mn, Ni, Co molar ratio sintering is prepared has the monocline stratiform Li that space group is C2/m
2MnO
3, space group is the rocking chair stratiform LiMn of R-3m
0.5-xNi
0.5-xCo
2xO
2With space group be the three-dimensional net structure spinelle LiMn of Fd3m
1.5-xNi
0.5-xCo
2xO
4Heterogeneous manganese based solid solution, then carry out compound with the grapheme material of nanometer high conductivity and make.
The preparation method of described heterogeneous manganese based solid solution composite positive pole may further comprise the steps:
(1) Li source compound, manganese source compound, nickel source compound and cobalt source compound are mixed, drying obtains the spheroidization presoma;
(2) the spheroidization presoma that step (1) is obtained carries out roasting, obtains heterogeneous manganese based solid solution;
(3) the heterogeneous manganese based solid solution surface recombination graphene layer that obtains in step (2) obtains heterogeneous manganese based solid solution composite positive pole.
It will be understood by those skilled in the art that as x=0(in the general formula of described heterogeneous manganese based solid solution and namely do not contain cobalt) time, step (1) does not add the cobalt source compound.
Preferably, the described mixing of step (1) comprises: raw material is added in the dispersant solution ball milling; Preferably, described dispersant solution is aqueous dispersant; Preferably, described ball milling adopts the roller ball grinding jar; Preferably, described ball milling speed is 100 ~ 800r/min, and more preferably 150 ~ 600r/min is particularly preferably 200 ~ 500r/min; Preferably, described Ball-milling Time is 1h at least, and more preferably 1.5 ~ 40h is particularly preferably 2 ~ 30h; Preferably, described dispersant is a kind or at least 2 kinds combination in butadiene-styrene rubber (SBR), polyvinyl alcohol (PVA), the carboxymethyl cellulose (CMC); Preferably, described dispersant is 0.05 ~ 4% of described heterogeneous manganese based solid solution gross mass, more preferably 0.08 ~ 3%, be particularly preferably 0.1～2%.
Preferably, the described drying of step (1) is spray drying.
Preferably, described Li source compound is lithium chloride, lithium bromide, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate, lithium sulfate, lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate, lithium oxalate, lithium formate, tert-butyl alcohol lithium, 1 kind or at least 2 kinds combination in lithium benzoate and the lithium citrate, the typical but non-limiting example of described combination comprises the combination of lithium chloride and lithium hydroxide, the combination of lithium bromide and lithium oxalate, the combination of lithium dihydrogen phosphate and lithium sulfate, lithium phosphate, the combination of phosphoric acid hydrogen two lithiums and lithium acetate, lithium sulfate, the combination of lithium hydroxide and lithium acetate, lithium carbonate, lithium nitrate, the combination of lithium oxalate and lithium formate, lithium oxalate, lithium formate, tert-butyl alcohol lithium, the combination of lithium benzoate and lithium citrate, lithium chloride, lithium bromide, lithium phosphate, phosphoric acid hydrogen two lithiums, the combination of lithium sulfate and lithium hydroxide etc.; Be particularly preferably a kind or at least 2 kinds combination in lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate, lithium oxalate, lithium formate, tert-butyl alcohol lithium, lithium benzoate and the lithium citrate.
Preferably, described manganese source compound is manganese phosphate, manganous hydroxide, manganese nitrate, manganese acetate, manganese oxalate, manganese carbonate, mangano-manganic oxide, manganese sesquioxide managnic oxide, 1 kind or at least 2 kinds combination in manganese dioxide and the hydroxyl oxidize manganese, the typical but non-limiting example of described combination comprises the combination of manganese phosphate and manganese acetate, the combination of manganous hydroxide and hydroxyl oxidize manganese, manganese nitrate, the combination of manganese acetate and manganese oxalate, manganous hydroxide, the combination of manganese nitrate and manganese acetate, mangano-manganic oxide, manganese sesquioxide managnic oxide, the combination of manganese dioxide and hydroxyl oxidize manganese, manganese phosphate, manganous hydroxide, mangano-manganic oxide, the combination of manganese sesquioxide managnic oxide and manganese dioxide etc.; Be particularly preferably a kind or at least 2 kinds combination in manganese nitrate, manganese acetate, manganese oxalate, manganese carbonate, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese dioxide and the hydroxyl oxidize manganese.
Preferably, described nickel source compound is, 1 kind or at least 2 kinds combination in nickel phosphate, nickel hydroxide, nickel nitrate, nickel acetate, nickel oxalate, nickelous carbonate and the nickel oxide, the typical but non-limiting example of described combination comprises the combination of nickel phosphate and nickel acetate, the combination of nickel hydroxide and hydroxy nickel oxide, the combination of nickel nitrate, nickel acetate and nickel oxalate, the combination of nickel hydroxide, nickel nitrate and nickel acetate, the combination of nickel oxide, nickel phosphate, nickel hydroxide and hydroxy nickel oxide, the combination of nickel phosphate, nickel hydroxide, nickel nitrate, nickel acetate and nickel oxalate etc.; Be particularly preferably a kind or at least 2 kinds combination in nickel nitrate, nickel acetate, nickel oxalate, nickelous carbonate, nickel oxide and the nickel hydroxide.
Preferably, described cobalt source compound is a kind or at least 2 kinds combination in cobalt nitrate, cobalt acetate, cobalt oxalate, cobalt carbonate, cobaltosic oxide and the cobalt hydroxide, the typical but non-limiting example of described combination comprises the combination of cobalt nitrate and cobalt acetate, the combination of cobalt oxalate and cobalt carbonate, the combination of cobalt carbonate, cobaltosic oxide and cobalt hydroxide, the combination of cobalt nitrate, cobalt acetate, cobalt oxalate and cobalt carbonate, the combination of cobalt acetate, cobalt oxalate, cobalt carbonate, cobaltosic oxide and cobalt hydroxide etc.
Preferably, sintering furnace is adopted in the described roasting of step (2).
Preferably, the programming rate of the described roasting of step (2) be 20 ℃/below the min, such as 0.1 ℃/min, 0.2 ℃/min, 0.5 ℃/min, 0.8 ℃/min, 0.9 ℃/min, 1.1 ℃/min, 1.5 ℃/min, 1.9 ℃/min, 2.1 ℃/min, 2.2 ℃/min, 2.5 ℃/min, 3 ℃/min, 5 ℃/min, 8 ℃/min, 9 ℃/min, 11 ℃/min, 13 ℃/min, 14 ℃/min, 16 ℃/min, 18 ℃/min, 19 ℃/min, 21 ℃/min, 25 ℃/min etc., more preferably 1～15 ℃/min is particularly preferably 2～10 ℃/min.
Preferably, the described sintering temperature of step (2) is 600 ~ 1100 ℃, more preferably 700 ~ 1050 ℃, is particularly preferably 750 ~ 1000 ℃.
Preferably, the described roasting time of step (2) is at least 4 hours, such as 4.1 hours, 4.2 hours, 4.5 hours, 4.9 hours, 5.1 hours, 5.2 hours, 5.5 hours, 5.9 hours, 6.1 hours, 7 hours, 8 hours, 10 hours, 15 hours, 20 hours, 25 hours, 30 hours, 31 hours, 33 hours, 35 hours, 38 hours, 39 hours, 41 hours, 45 hours etc., more preferably 5 ~ 40 hours, be particularly preferably 6 ~ 32 hours.
Preferably, the described roasting of step (2) is carried out under oxidizing atmosphere, particularly preferably in carrying out under air and/or the oxygen atmosphere; Preferably, the flow of described oxidizing atmosphere is 2 ~ 150mL/min, and more preferably 3 ~ 120mL/min is particularly preferably 5 ~ 100mL/min.
Preferably, cool off after the described roasting of step (2) is finished; Preferably, described being cooled to naturally cools to room temperature.
Preferably, pulverizing after the described roasting of step (2) is finished, classification, screening obtain heterogeneous manganese based solid solution.
Preferably, the described Combined Mining spray drying process of step (3); Preferably, described spray drying process comprises: the suspension-turbid liquid of heterogeneous manganese based solid solution material slowly is added in the graphene dispersing solution, mixes, spray drying obtains heterogeneous manganese based solid solution composite positive pole; Preferably, the suspension-turbid liquid of described heterogeneous manganese based solid solution material contains surfactant; Preferably, the solvent of the suspension-turbid liquid of described heterogeneous manganese based solid solution material is water; Preferably, described surfactant is a kind or at least 2 kinds combination in stearic acid, neopelex, fatty glyceride, amino acid, lecithin, aliphatic acid sorb smooth (sapn), polysorbate (Tween-60), polyoxyethylene and the polyoxypropylene; Preferably, the mass ratio of described surfactant and heterogeneous manganese based solid solution material is 0.05:100 ~ 10:100, is particularly preferably 0.08:100 ~ 8:100, is particularly preferably 0.1:100～5:100; Preferably, the solvent of described graphene dispersing solution is a kind or at least 2 kinds combination in water, ethanol, methyl alcohol, glycerine, acetone, oxolane, benzene or the toluene; The typical but non-limiting preparation method of described graphene dispersing solution can comprise: takes by weighing a certain amount of Graphene and joins in an amount of solvent, and ultrasonic 20～100min, electric stirring 2～10h is mixed with graphene dispersing solution.
The preparation method of described heterogeneous manganese based solid solution composite positive pole may further comprise the steps:
(1) with Li source compound, manganese source compound, nickel source compound and cobalt source compound, join successively in the aqueous solution of dispersant, be stirred to the formation suspension-turbid liquid, suspension-turbid liquid ground with the rotating speed of 100 ~ 800r/min made slurry at least in 1 hour, adopt spray dryer that described slurry is carried out spray drying, make manganese, nickel, the equally distributed spheroidization presoma of three kinds of metallic elements of cobalt;
(2) the spheroidization presoma that step (1) is obtained places sintering furnace, with the following programming rate of 20 ℃/min, be warmed up in 600～1100 ℃ of scopes, be incubated at least 4 hours, in roasting process, pass into continuously simultaneously oxidizing atmosphere, flow velocity is 2 ~ 150mL/min, naturally cools to room temperature after the roasting, and obtains heterogeneous manganese based solid solution through pulverizing, classification, screening;
(3) under agitation, the heterogeneous manganese based solid solution material adding that step (2) is obtained contains in the aqueous solution of surfactant, form suspension-turbid liquid, slowly join suspension-turbid liquid in the graphene dispersing solution, fully stir and form heterogeneous manganese based solid solution/Graphene mixed slurry, adopt spray dryer that mixed slurry is carried out spray drying, obtain heterogeneous manganese based solid solution composite positive pole.
By the method for the invention, having space group is the monocline stratiform Li of C2/m
2MnO
3, space group is the rocking chair stratiform LiMn of R-3m
0.5-xNi
0.5-xCo
2xO
2With space group be the three-dimensional net structure spinelle LiMn of Fd3m
1.5-xNi
0.5-xCo
2xO
4Three-phase forms solid solution, has greatly accelerated Li
+Embedding and deviate from speed, significantly improved the intrinsic ionic conductivity of solid solution, first coulombic efficiency and the cryogenic property of solid solution are improved significantly; Form uniform graphene layer by spray drying on the solid solution surface simultaneously, and adopt surfactant so that have preferably adhesion between solid solution and Graphene, greatly reduce interface contact resistance between the two, improved the intrinsic electronic conductivity of solid-solution material, the high rate performance of heterogeneous manganese based solid solution composite material is significantly improved.
Compared with prior art, the beneficial effect of a kind of heterogeneous manganese based solid solution composite positive pole of the present invention and preparation method thereof is as follows:
(1) heterogeneous manganese based solid solution aLiMn of the present invention
1.5-xNi
0.5-xCo
2XO
4BLi
2MnO
3CLiMn
0.5-xNi
0.5-xCo
2xO
2, 0≤x＜0.5 wherein, a:b:c is (0 ~ 0.5): (0.1 ~ 0.7): (0.1 ~ 0.7), and 0＜a≤0.5, a+b+c=1 is except having the Li in the conventional manganese sill
2MnO
3And LiMO
2(M=Ni, Co, Mn) mutually outside, also by control Li/M(M=Mn, Ni, Co) to have introduced space group be the LiMn of Fd3m for molar ratio and Mn, Ni, Co molar ratio
1.5-xNi
0.5-xCo
2xO
4Phase, this crystalline phase has been accelerated Li greatly owing to having abundant three-dimensional network spinel structure
+Embedding and deviate from speed, significantly improved the intrinsic ionic conductivity of solid solution, first coulombic efficiency and the cryogenic property of solid solution are improved significantly;
(2) the present invention is on the basis of the heterogeneous manganese based solid solution of preparation, by spray-dired mode, realized the even coating of Graphene on the solid solution surface, simultaneously owing in spray process, having added surfactant, so that have preferably adhesion between solid solution and Graphene, greatly reduce interface contact resistance between the two, improved the intrinsic electronic conductivity of solid-solution material, the high rate performance of heterogeneous manganese based solid solution composite material is significantly improved;
(3) heterogeneous manganese based solid solution composite positive pole of the present invention has that coulombic efficiency is high first, good with the negative material matching, energy density is high, and charge and discharge under the condition advantages such as the good and high rate performance of Stability Analysis of Structures is superior at high voltage, specific discharge capacity is up to 268mAh/g, capacity than cobalt acid lithium and LiFePO4 is high by 60%, and first charge-discharge efficiency reaches 85%, and with hard carbon and silicon-carbon class high power capacity negative material good matching is arranged; Under the 2C multiplying power, specific discharge capacity still reaches 190mAh/g, and high rate performance significantly improves; Under-20 ℃ of cryogenic conditions, capability retention is more than 70%.
Description of drawings
Fig. 1 is the SEM figure of the presoma of the embodiment of the invention 2 preparations.
Fig. 2 (a) is the profile of the presoma of the embodiment of the invention 2 preparations; Fig. 2 (b) is the mapping of nickel element in the presoma of the embodiment of the invention 2 preparation; Fig. 2 (c) is the mapping of cobalt element in the presoma of the embodiment of the invention 2 preparation; Fig. 2 (d) is the mapping of manganese element in the presoma of the embodiment of the invention 2 preparation.
Fig. 3 (a) is the XRD collection of illustrative plates of the positive electrode of the embodiment of the invention 2, Comparative Examples 1 and Comparative Examples 2 preparations; Wherein, a is the positive electrode of embodiment 2 preparations, and b is the positive electrode of Comparative Examples 1 preparation, and c is the positive electrode of Comparative Examples 2 preparations.
Fig. 4 is the FE-SEM figure of raw materials used Graphene in the embodiment of the invention.
Fig. 5 (a) is the FE-SEM figure of the composite positive pole of the embodiment of the invention 2 preparations; Fig. 5 (b) is the FE-SEM figure of the positive electrode of Comparative Examples 2 preparations.
Fig. 6 is the charging and discharging curve figure of the positive electrode of the embodiment of the invention 2, Comparative Examples 1 and Comparative Examples 2 preparations; Wherein, a is the positive electrode of embodiment 2 preparations, and b is the positive electrode of Comparative Examples 1 preparation, and c is the positive electrode of Comparative Examples 2 preparations.
Fig. 7 is the high rate performance curve chart of the embodiment of the invention 1～7 and Comparative Examples 1～2, and wherein, a, b, c, d, e, f and g respectively are the positive electrode of embodiment 1～7 preparation; H and i are respectively the positive electrode of Comparative Examples 1 and Comparative Examples 2 preparations.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
With lithium hydroxide 14mo1, manganese nitrate 7mol, nickel nitrate 2mo1, cobalt nitrate 1mo1 evenly mix and are dispersed in the cmc soln, are stirred to the formation suspension-turbid liquid; Suspension-turbid liquid is transferred in the roller ball grinding jar, grinds 5h with the rotating speed of 400r/min and make viscous paste; Adopt spray dryer that above-mentioned slurry is carried out spray drying, make manganese, nickel, the equally distributed spherical presoma of three kinds of metallic elements of cobalt; Presoma is placed sintering furnace, programming rate with 5 ℃/min, be warmed up to 950 ℃, insulation 10h, in roasting process, pass into continuously dry air, flow velocity is 20mL/min, naturally cools to room temperature after the roasting, and obtains heterogeneous manganese based solid solution positive electrode 0.05LiMn through pulverizing, classification, screening
1.4Ni
0.4Co
0.2O
40.475Li
2MnO
30.475LiMn
0.4Ni
0.4Co
0.2O
2Be that 2:100 takes by weighing a certain amount of Graphene and joins in the ethanol by Graphene and heterogeneous manganese based solid solution positive electrode mass ratio, ultrasonic 30min, electric stirring 2h is mixed with graphene dispersing solution; Under electric stirring, it is in the Tween-60 aqueous solution of 0.2:100 that heterogeneous manganese based solid solution positive electrode is joined the mass ratio that contains with heterogeneous manganese based solid solution material, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in the graphene dispersing solution, fully stir and form heterogeneous manganese based solid solution/Graphene mixed slurry; Adopt spray dryer that mixed slurry is carried out spray drying, obtain 0.05LiMn
1.4Ni
0.4Co
0.2O
40.475Li
2MnO
30.475LiMn
0.4Ni
0.4Co
0.2O
2Composite positive pole.
Embodiment 2
With lithium hydroxide 13.2mo1, manganese nitrate 7mol, nickel nitrate 2mol, cobalt nitrate 1mo1 evenly mix and are dispersed in the PVA aqueous solution, are stirred to the formation suspension-turbid liquid; Suspension-turbid liquid is transferred in the roller ball grinding jar, grinds 5h with the rotating speed of 400r/min and make viscous paste; Adopt spray dryer that above-mentioned slurry is carried out spray drying, make manganese, nickel, the equally distributed spherical presoma of three kinds of metallic elements of cobalt; Presoma is placed sintering furnace, programming rate with 5 ℃/min, be warmed up to 950 ℃, insulation 10h, in roasting process, pass into continuously simultaneously dry air, flow velocity is 20mL/min, naturally cools to room temperature after the roasting, and obtains heterogeneous manganese based solid solution positive electrode 0.1LiMn through pulverizing, classification, screening
1.4Ni
0.4Co
0.2O
40.45Li
2MnO
30.45LiMn
0.4Ni
0.4Co
0.2O
2Be that 2:100 takes by weighing a certain amount of Graphene and joins in the ethanol by Graphene and heterogeneous manganese based solid solution positive electrode mass ratio, ultrasonic 30min, electric stirring 2h is mixed with graphene dispersing solution; Under electric stirring, it is in the Tween-60 aqueous solution of 0.2:100 that heterogeneous manganese based solid solution positive electrode is joined the mass ratio that contains with heterogeneous manganese based solid solution material, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in the graphene dispersing solution, fully stir and form heterogeneous manganese based solid solution/Graphene mixed slurry; Adopt spray dryer that mixed slurry is carried out spray drying, make 0.1LiMn
1.4Ni
0.4Co
0.2O
40.45Li
2MnO
30.45LiMn
0.4Ni
0.4Co
0.2O
2Composite positive pole.
Embodiment 3
With lithium hydroxide 11.7mo1, manganese nitrate 7mol, nickel nitrate 2mo1, cobalt nitrate 1mo1 evenly mix and are dispersed in the cmc soln, are stirred to the formation suspension-turbid liquid.Suspension-turbid liquid is transferred in the roller ball grinding jar, grinds 5h with the rotating speed of 400r/min and make viscous paste.Adopt spray dryer that above-mentioned slurry is carried out spray drying, make manganese, nickel, the equally distributed spherical presoma of three kinds of metallic elements of cobalt, presoma is put in the sintering furnace, with the programming rate of 5 ℃/min, be warmed up to 950 ℃, insulation 10h, in roasting process, pass into continuously simultaneously dry air, flow velocity is 20mL/min, naturally cools to room temperature after the roasting, and obtains heterogeneous manganese based solid solution positive electrode 0.2LiMn through pulverizing, classification, screening
1.4Ni
0.4Co
0.2O
40.4Li
2MnO
30.4LiMn
0.4Ni
0.4Co
0.2O
2Be that 5:100 takes by weighing a certain amount of Graphene and joins in the ethanol by Graphene and heterogeneous manganese based solid solution positive electrode mass ratio, ultrasonic 30min, electric stirring 2h is mixed with graphene dispersing solution.Under electric stirring, heterogeneous manganese based solid solution positive electrode is joined in the aqueous solution of Tween-60 that the mass ratio that contains with heterogeneous manganese based solid solution material is 0.2:100, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in the graphene dispersing solution, fully stir and form heterogeneous manganese based solid solution/Graphene mixed slurry.Adopt spray dryer that slurry is carried out spray drying, make 0.2LiMn
1.4Ni
0.4Co
0.2O
40.4Li
2MnO
30.4LiMn
0.4Ni
0.4Co
0.2O
2Composite positive pole.
With lithium nitrate 13.2mo1, manganese acetate 6.5mol, nickel acetate 1.5mo1, cobalt acetate 2.0mo1 evenly mix and are dispersed in the PVA aqueous solution, are stirred to the formation suspension-turbid liquid, grind 5h with the rotating speed of 400r/min and make viscous paste.Adopt spray dryer that above-mentioned slurry is carried out spray drying, make manganese, nickel, the equally distributed spherical presoma of three kinds of metallic elements of cobalt.Presoma is put in the sintering furnace, programming rate with 5 ℃/min, be warmed up to 950 ℃, insulation 10h, in roasting process, pass into continuously simultaneously dry air, flow velocity is 20mL/min, naturally cools to room temperature after the roasting, and obtains heterogeneous manganese based solid solution positive electrode 0.1LiMn through pulverizing, classification, screening
1.3Ni
0.3Co
0.4O
40.45Li
2MnO
30.45LiMn
0.3Ni
0.3Co
0.4O
2Be that 10:100 takes by weighing a certain amount of Graphene and joins in the ethanol by Graphene and heterogeneous manganese based solid solution positive electrode mass ratio, ultrasonic 30min, electric stirring 2h is mixed with graphene dispersing solution.Under electric stirring, heterogeneous manganese based solid solution positive electrode is joined in the aqueous solution of Tween-60 that the mass ratio that contains with heterogeneous manganese based solid solution material is 0.2:100, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in the graphene dispersing solution, fully stir and form heterogeneous manganese based solid solution/Graphene mixed slurry; Adopt spray dryer that slurry is carried out spray drying, make 0.1LiMn
1.3Ni
0.3Co
0.4O
40.45Li
2MnO
30.45LiMn
0.3Ni
0.3Co
0.4O
2Composite positive pole.
Embodiment 5
With lithium acetate 13.2mo1, manganese acetate 6.67mol, nickel acetate 1.65mo1, cobalt acetate 1.65mo1 evenly mix and are dispersed in the cmc soln, are stirred to the formation suspension-turbid liquid.Suspension-turbid liquid is transferred in the roller ball grinding jar, grinds 5h with the rotating speed of 400r/min and make viscous paste.Adopt spray dryer that above-mentioned slurry is carried out spray drying, make manganese, nickel, the equally distributed spherical presoma of three kinds of metallic elements of cobalt.Presoma is put in the sintering furnace, programming rate with 5 ℃/min, be warmed up to 950 ℃, insulation 10h, in roasting process, pass into continuously simultaneously dry air, flow velocity is 20mL/min, naturally cools to room temperature after the roasting, and obtains heterogeneous manganese based solid solution positive electrode 0.1LiMn through pulverizing, classification, screening
1.33Ni
0.33Co
0.333O
40.45Li
2MnO
30.45LiMn
0.333Ni
0.333Co
0.333O
2Be that 2:100 takes by weighing a certain amount of Graphene and joins in the ethanol by Graphene and heterogeneous manganese based solid solution positive electrode mass ratio, ultrasonic 30min, electric stirring 2h is mixed with graphene dispersing solution.Under electric stirring, heterogeneous manganese based solid solution positive electrode is joined in the aqueous solution of Tween-60 that the mass ratio that contains with heterogeneous manganese based solid solution material is 0.2:100, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in the graphene dispersing solution, fully stir and form heterogeneous manganese based solid solution/Graphene mixed slurry.Adopt spray dryer that mixed slurry is carried out spray drying, make 0.1LiMn
1.33Ni
0.33Co
0.333O
40.45Li
2MnO
30.45LiMn
0.333Ni
0.333Co
0.333O
2Composite positive pole.
Embodiment 6
With lithium acetate 13.2mo1, manganese acetate 7.25mol, nickel acetate 2.25mo1, cobalt acetate 0.50mo1 evenly mix and are dispersed in the PVA solution, are stirred to the formation suspension-turbid liquid.Suspension-turbid liquid is transferred in the roller ball grinding jar, grinds 5h with the rotating speed of 400r/min and make viscous paste.Adopt spray dryer that above-mentioned slurry is carried out spray drying, make manganese, nickel, the equally distributed spherical presoma of three kinds of metallic elements of cobalt.Presoma is put in the sintering furnace, programming rate with 5 ℃/min, be warmed up to 950 ℃, insulation 10h, in roasting process, pass into continuously simultaneously dry air, flow velocity is 20mL/min, naturally cools to room temperature after the roasting, and obtains heterogeneous manganese based solid solution positive electrode 0.1LiMn through pulverizing, classification, screening
1.45Ni
0.45Co
0.1O
40.45Li
2MnO
30.45LiMn
0.45Ni
0.45Co
0.1O
2Be that 0.1:100 takes by weighing a certain amount of Graphene and joins in the ethanol by Graphene and heterogeneous manganese based solid solution positive electrode mass ratio, ultrasonic 30min, electric stirring 2h, be mixed with graphene dispersing solution, under electric stirring, heterogeneous manganese based solid solution positive electrode is joined in the aqueous solution of Tween-60 that the mass ratio that contains with heterogeneous manganese based solid solution material is 0.1:100, form suspension-turbid liquid, slowly join suspension-turbid liquid in the graphene dispersing solution, fully stir and form heterogeneous manganese based solid solution/Graphene mixed slurry, adopt spray dryer that slurry is carried out spray drying, make 0.1LiMn
1.45Ni
0.45Co
0.1O
40.45Li
2MnO
30.45LiMn
0.45Ni
0.45Co
0.1O
2Composite positive pole.
Embodiment 7
With lithium acetate 13.2mo1, manganese acetate 7.5mol, nickel acetate 2.5mo1 evenly mix and are dispersed in the cmc soln, are stirred to the formation suspension-turbid liquid.Suspension-turbid liquid is transferred in the roller ball grinding jar, grinds 5h with the rotating speed of 400r/min and make viscous paste.Adopt spray dryer that above-mentioned slurry is carried out spray drying, make manganese, the equally distributed spherical presoma of two kinds of metallic elements of nickel, presoma is put in the sintering furnace, with the programming rate of 5 ℃/min, be warmed up to 950 ℃, insulation 10h, in roasting process, pass into continuously simultaneously dry air, flow velocity is 20mL/min, naturally cools to room temperature after the roasting, and obtains heterogeneous manganese based solid solution 0.1LiMn through pulverizing, classification, screening
1.5Ni
0.5O
40.45Li
2MnO
30.45LiMn
0.5Ni
0.5O
2Be that 10:100 takes by weighing a certain amount of Graphene and joins in the ethanol by Graphene and heterogeneous manganese based solid solution positive electrode mass ratio, ultrasonic 30min, electric stirring 2h is mixed with graphene dispersing solution.Under electric stirring, heterogeneous manganese based solid solution positive electrode is joined in the aqueous solution of Tween-60 that the mass ratio that contains with heterogeneous manganese based solid solution material is 5:100, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in the graphene dispersing solution, fully stir and form heterogeneous manganese based solid solution/Graphene mixed slurry.Adopt spray dryer that slurry is carried out spray drying, make 0.3LiMn
1.5Ni
0.5O
40.2Li
2MnO
30.5LiMn
0.5Ni
0.5O
2Composite positive pole.
Embodiment 8
With lithium oxalate 11mo1, mangano-manganic oxide 6.09mol, nickel hydroxide 0.09mo1, cobalt hydroxide 8.82mo1 evenly mix and are dispersed in the PVA solution, are stirred to the formation suspension-turbid liquid.Suspension-turbid liquid is transferred in the roller ball grinding jar, grinds 1h with the rotating speed of 800r/min and make viscous paste.Adopt spray dryer that above-mentioned slurry is carried out spray drying, make manganese, nickel, the equally distributed spherical presoma of three kinds of metallic elements of cobalt.Presoma is put in the sintering furnace, programming rate with 20 ℃/min, be warmed up to 1100 ℃, insulation 4h, in roasting process, pass into continuously simultaneously dry air, flow velocity is 150mL/min, naturally cools to room temperature after the roasting, and obtains heterogeneous manganese based solid solution positive electrode 0.5LiMn through pulverizing, classification, screening
1.01Ni
0.01Co
0.98O
40.1Li
2MnO
30.4LiMn
0.01Ni
0.01Co
0.98O
2Be that 0.05:100 takes by weighing a certain amount of Graphene and joins in the deionized water by Graphene and heterogeneous manganese based solid solution positive electrode mass ratio, ultrasonic 15min, electric stirring 20h, be mixed with graphene dispersing solution, under electric stirring, heterogeneous manganese based solid solution positive electrode is joined in the aqueous solution of lecithin that the mass ratio that contains with heterogeneous manganese based solid solution material is 0.05:100, form suspension-turbid liquid, slowly join suspension-turbid liquid in the graphene dispersing solution, fully stir and form heterogeneous manganese based solid solution/Graphene mixed slurry, adopt spray dryer that slurry is carried out spray drying, make 0.5LiMn
1.01Ni
0.01Co
0.98O
40.1Li
2MnO
30.4LiMn
0.01Ni
0.01Co
0.98O
2Composite positive pole.
Embodiment 9
With phosphoric acid hydrogen two lithium 12.9mo1, manganous hydroxide 6.479mol, nickel oxide 3.479mo1, cobalt oxalate 0.142mo1 evenly mix and are dispersed in the cmc soln, are stirred to the formation suspension-turbid liquid; Suspension-turbid liquid is transferred in the roller ball grinding jar, grinds 15h with the rotating speed of 100r/min and make viscous paste; Adopt spray dryer that above-mentioned slurry is carried out spray drying, make manganese, nickel, the equally distributed spherical presoma of three kinds of metallic elements of cobalt; Presoma is placed sintering furnace, programming rate with 1 ℃/min, be warmed up to 600 ℃, insulation 40h, in roasting process, pass into continuously dry air, flow velocity is 2mL/min, naturally cools to room temperature after the roasting, and obtains heterogeneous manganese based solid solution positive electrode 0.01LiMn through pulverizing, classification, screening
1.49Ni
0.49Co
0.02O
40.29Li
2MnO
30.7LiMn
0.49Ni
0.49Co
0.02O
2Be that 20:100 takes by weighing a certain amount of Graphene and joins in the ethanol by Graphene and heterogeneous manganese based solid solution positive electrode mass ratio, ultrasonic 18min, electric stirring 10h is mixed with graphene dispersing solution; Under electric stirring, heterogeneous manganese based solid solution positive electrode is joined in the aqueous solution of neopelex that the mass ratio that contains with heterogeneous manganese based solid solution material is 10:100, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in the graphene dispersing solution, fully stir and form heterogeneous manganese based solid solution/Graphene mixed slurry; Adopt spray dryer that mixed slurry is carried out spray drying, obtain 0.01LiMn
1.49Ni
0.49Co
0.02O
40.29Li
2MnO
30.7LiMn
0.49Ni
0.49Co
0.02O
2Composite positive pole.
With lithium chloride 17mo1, manganese carbonate 9.3mol, nickel phosphate 0.3mo1, cobaltosic oxide 2.4mo1 evenly mix and are dispersed in the cmc soln, are stirred to the formation suspension-turbid liquid.Suspension-turbid liquid is transferred in the roller ball grinding jar, grinds 10h with the rotating speed of 150r/min and make viscous paste.Adopt spray dryer that above-mentioned slurry is carried out spray drying, make manganese, nickel, the equally distributed spherical presoma of three kinds of metallic elements of cobalt, presoma is put in the sintering furnace, with the programming rate of 15 ℃/min, be warmed up to 1050 ℃, insulation 5h, in roasting process, pass into continuously simultaneously dry air, flow velocity is 3mL/min, naturally cools to room temperature after the roasting, and obtains heterogeneous manganese based solid solution positive electrode 0.2LiMn through pulverizing, classification, screening
1.1Ni
0.1Co
0.8O
40.7Li
2MnO
30.1LiMn
0.1Ni
0.1Co
0.8O
2Be that 15:100 takes by weighing a certain amount of Graphene and joins in the toluene by Graphene and heterogeneous manganese based solid solution positive electrode mass ratio, ultrasonic 20min, electric stirring 6h is mixed with graphene dispersing solution.Under electric stirring, heterogeneous manganese based solid solution positive electrode is joined in the aqueous solution of polyoxypropylene that the mass ratio that contains with heterogeneous manganese based solid solution material is 0.07:100, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in the graphene dispersing solution, fully stir and form heterogeneous manganese based solid solution/Graphene mixed slurry.Adopt spray dryer that slurry is carried out spray drying, make 0.2LiMn
1.1Ni
0.1Co
0.8O
40.7Li
2MnO
30.1LiMn
0.1Ni
0.1Co
0.8O
2Composite positive pole.
Comparative Examples 1
With lithium hydroxide 15mo1, manganese nitrate 7mol, nickel nitrate 2mo1, cobalt nitrate 1mo1 evenly mix and are dispersed in the cmc soln, are stirred to the formation suspension-turbid liquid; Suspension-turbid liquid is transferred in the roller ball grinding jar, grinds 5h with the rotating speed of 400r/min and make viscous paste.Adopt spray dryer that above-mentioned slurry is carried out spray drying, the inlet temperature of spray dryer is 250 ℃, and outlet temperature is 120 ℃, and charging rate is 20mL/min, makes manganese, nickel, the equally distributed spherical presoma of three kinds of metallic elements of cobalt by spraying.Presoma is put in the sintering furnace, programming rate with 5 ℃/min, be warmed up to 950 ℃, insulation 10h, in roasting process, pass into continuously simultaneously dry air, flow velocity is 20mL/min, naturally cools to room temperature after the roasting, and obtains heterogeneous manganese based solid solution positive electrode 0.5Li through pulverizing, classification, screening
2MnO
30.5LiMn
0.4Ni
0.4Co
0.2O
2
Comparative Examples 2
With lithium hydroxide 13.2mo1, manganese nitrate 7mol, nickel nitrate 2mo1, cobalt nitrate 1mo1 evenly mix and are dispersed in the cmc soln, are stirred to the formation suspension-turbid liquid.Suspension-turbid liquid is transferred in the roller ball grinding jar, grinds 5h with the rotating speed of 400r/min and make viscous paste; Adopt spray dryer that above-mentioned slurry is carried out spray drying, the inlet temperature of spray dryer is 250 ℃, and outlet temperature is 120 ℃, and charging rate is 20mL/min, makes manganese, nickel, the equally distributed spherical presoma of three kinds of metallic elements of cobalt by spraying.Presoma is placed sintering furnace, programming rate with 5 ℃/min, be warmed up to 950 ℃, insulation 10h, in roasting process, pass into continuously dry air, flow velocity is 20mL/min, naturally cools to room temperature after the roasting, and obtains heterogeneous manganese based solid solution positive electrode 0.1LiMn through pulverizing, classification, screening
1.4Ni
0.4Co
0.2O
40.45Li
2MnO
30.45LiMn
0.4Ni
0.4Co
0.2O
2
The positive electrode that embodiment 1-10 and Comparative Examples 1 ~ 2 obtain is tested.
Fig. 1 is the SEM figure of the presoma in the embodiment of the invention 2.As shown in Figure 1, the presoma particle diameter is evenly distributed, and is good spherical pattern.
Fig. 2 is the profile of presoma in the embodiment of the invention 2 and Ni, Co, Mn mapping.As shown in Figure 2, manganese, nickel and manganese element evenly distribute spheric granules is inner, illustrates that the molecule rank that presoma that drying process with atomizing prepares can the realization response raw material evenly mixes.
Fig. 3 is the XRD collection of illustrative plates of the embodiment of the invention 2, Comparative Examples 1 and Comparative Examples 2.As shown in Figure 3, the 0.5Li of preparation in the Comparative Examples 1
2MnO
30.5LiMn
0.4Ni
0.4Co
0.2O
2Material contains the monocline stratiform Li that space group is C2/m
2MnO
3With space group be the rocking chair stratiform LiMn of R-3m
0.5-xNi
0.5-xCo
2xO
2The characteristic diffraction peak of two crystalline phases.By contrast, the 0.1LiMn of Comparative Examples 2 preparations
1.4Ni
0.4Co
0.2O
40.45Li
2MnO
30.45LiMn
0.4Ni
0.4Co
0.2O
2Material is the three-phase solid-solution material, and the characteristic diffraction peak of its material in having Comparative Examples 1, space group also having occurred is the three-dimensional net structure high-voltage spinel LiMn of Fd3m
1.5-xNi
0.5-xCo
2xO
4The characteristic peak of phase.Compare the 0.1LiMn of embodiment 2 preparations with Comparative Examples 2
1.4Ni
0.4Co
0.2O
40.45Li
2MnO
30.45LiMn
0.4Ni
0.4Co
0.2O
2Composite positive pole the characteristic diffraction peak of graphite occurred simultaneously about 25 ° except the characteristic diffraction peak that has three solid solution phases.
Fig. 4 is the FE-SEM figure of raw materials used Graphene in the embodiment of the invention.As seen from the figure, the used grapheme material of the present invention has the multi-layer nano sheet-like morphology, and structure is preserved comparatively complete.
Fig. 5 is the SEM figure of the embodiment of the invention 2 and Comparative Examples 2.Contrasting two figure can find out, before the Graphene of not spraying, the surface of primary particle is comparatively smooth, and through after the spraying Graphene step, it is coarse that particle surface becomes, and coated the uniform flake graphite alkene of one deck material on the surface of heterogeneous manganese based solid solution.
Fig. 6 is the charging and discharging curve figure of the embodiment of the invention 2, Comparative Examples 1 and Comparative Examples 2.As can be seen from the figure, the 0.1LiMn among the embodiment 2
1.4Ni
0.4Co
0.20.45Li
2MnO
30.45LiMn
0.4Ni
0.4Co
0.2O
2/ grapheme composite positive electrode material first discharge specific capacity reaches 268.4mAh/g, and efficient has reached 85.7% first, obviously is better than and does not mix high-voltage spinel LiMn in the Comparative Examples 1
1.4Ni
0.4Co
0.2O
4Mutually with the 0.5Li that does not carry out the graphene coated processing
2MnO
30.5LiMn
0.4Ni
0.4Co
0.2O
2Do not carry out graphene coated in positive electrode and the Comparative Examples 2 and process 0.1LiMn
1.4Ni
0.4Co
0.2O
40.45Li
2MnO
30.45LiMn
0.4Ni
0.4Co
0.2O
2Positive electrode, explanation is through introducing high-voltage spinel LiMn thus
1.4Ni
0.4Co
0.2O
4Mutually and carry out the Graphene surface coat process after, the specific discharge capacity of composite material has had raising to a certain degree, first charge-discharge efficiency then significantly improves.
Fig. 7 is the high rate performance curve chart of the embodiment of the invention 1～7, Comparative Examples 1～2.As can be seen from the figure, through introducing high-voltage spinel LiMn
1.4Ni
0.4Co
0.2O
4Mutually and carry out the Graphene surface coat process after, the high rate performance of composite material is significantly improved.
Table 1 is the simulated battery test result of embodiment 1～9 and Comparative Examples 1～2.
Table 1
Can find out from table 1 contrast, through introducing high-voltage spinel LiMn
1.4Ni
0.4Co
0.2O
4Phase, material has obtained obvious improvement at the lower capability retention of low temperature (20 ℃), brings up to 60.2% in the Comparative Examples 2 by 35.4% in the Comparative Examples 1, and after processing through graphene coated, the further raising of having got back of material capability retention at low temperatures.In addition, it can also be seen that from table, after processing through graphene coated, the material cyclical stability among the embodiment significantly improves, the capacity of material 80% having brought up to about 95% when not coating after 50 all charge and discharge cycles.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. a heterogeneous manganese based solid solution composite positive pole comprises heterogeneous manganese based solid solution and Graphene, and wherein, described heterogeneous manganese based solid solution comprises Li
2MnO
3, LiMn
0.5-xNi
0.5-xCo
2xO
2And LiMn
1.5-xNi
0.5-xCo
2xO
4Three-phase, 0≤x＜0.5.
2. heterogeneous manganese based solid solution composite positive pole as claimed in claim 1 is characterized in that, the general formula of described heterogeneous manganese based solid solution is aLiMn
1.5-xNi
0.5-xCo
2xO
4BLi
2MnO
3CLiMn
0.5-xNi
0.5-xCo
2xO
2, 0≤x＜0.5 wherein, a:b:c is (0 ~ 0.5): (0.1 ~ 0.7): (0.1 ~ 0.7), and 0＜a≤0.5, a+b+c=1;
Preferably, described a:b:c is (0 ~ 0.3): (0.3 ~ 0.6): (0.3 ~ 0.6), and 0＜a≤0.3, a+b+c=1, particularly preferably, described a:b:c is (0 ~ 0.2): (0.4 ~ 0.5): (0.4 ~ 0.5), and 0＜a≤0.2, b=c, a+b+c=1;
Preferably, the mass ratio that described Graphene accounts for heterogeneous manganese based solid solution is 0.05:100 ~ 20:100,0.08:100 ~ 15:100 more preferably, 0.1:100 ~ 10:100.
3. the preparation method of a heterogeneous manganese based solid solution composite positive pole as claimed in claim 1 or 2 may further comprise the steps:
(1) Li source compound, manganese source compound, nickel source compound and cobalt source compound are mixed, drying obtains the spheroidization presoma;
(2) the spheroidization presoma that step (1) is obtained carries out roasting, obtains heterogeneous manganese based solid solution;
(3) the heterogeneous manganese based solid solution surface recombination graphene layer that obtains in step (2) obtains heterogeneous manganese based solid solution composite positive pole.
4. method as claimed in claim 3 is characterized in that, the described mixing of step (1) comprises: raw material is added in the dispersant solution ball milling;
Preferably, described dispersant solution is aqueous dispersant;
Preferably, described ball milling adopts the roller ball grinding jar;
Preferably, described ball milling speed is 100 ~ 800r/min, and more preferably 150 ~ 600r/min is particularly preferably 200 ~ 500r/min;
Preferably, described Ball-milling Time is 1h at least, and more preferably 1.5 ~ 40h is particularly preferably 2 ~ 30h;
Preferably, described dispersant is a kind or at least 2 kinds combination in butadiene-styrene rubber, polyvinyl alcohol, the carboxymethyl cellulose;
Preferably, described dispersant is 0.05 ~ 4% of described heterogeneous manganese based solid solution gross mass, more preferably 0.08 ~ 3%, be particularly preferably 0.1～2%;
Preferably, the described drying of step (1) is spray drying.
5. such as claim 3 or 4 described methods, it is characterized in that, described Li source compound is a kind or at least 2 kinds combination in lithium chloride, lithium bromide, lithium phosphate, phosphoric acid hydrogen two lithiums, lithium dihydrogen phosphate, lithium sulfate, lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate, lithium oxalate, lithium formate, tert-butyl alcohol lithium, lithium benzoate and the lithium citrate, is particularly preferably a kind or at least 2 kinds combination in lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate, lithium oxalate, lithium formate, tert-butyl alcohol lithium, lithium benzoate and the lithium citrate;
Preferably, described manganese source compound is a kind or at least 2 kinds combination in manganese phosphate, manganous hydroxide, manganese nitrate, manganese acetate, manganese oxalate, manganese carbonate, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese dioxide and the hydroxyl oxidize manganese, is particularly preferably a kind or at least 2 kinds combination in manganese nitrate, manganese acetate, manganese oxalate, manganese carbonate, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese dioxide and the hydroxyl oxidize manganese.
6. such as each described method of claim 3-5, it is characterized in that, described nickel source compound is, 1 kind or at least 2 kinds combination in nickel phosphate, nickel hydroxide, nickel nitrate, nickel acetate, nickel oxalate, nickelous carbonate and the nickel oxide are particularly preferably a kind or at least 2 kinds combination in nickel nitrate, nickel acetate, nickel oxalate, nickelous carbonate, nickel oxide and the nickel hydroxide;
Preferably, described cobalt source compound is a kind or at least 2 kinds combination in cobalt nitrate, cobalt acetate, cobalt oxalate, cobalt carbonate, cobaltosic oxide and the cobalt hydroxide.
7. such as each described method of claim 3-6, it is characterized in that, sintering furnace is adopted in the described roasting of step (2);
Preferably, the programming rate of the described roasting of step (2) be 20 ℃/below the min, more preferably 1～15 ℃/min is particularly preferably 2～10 ℃/min;
Preferably, the described sintering temperature of step (2) is 600 ~ 1100 ℃, more preferably 700 ~ 1050 ℃, is particularly preferably 750 ~ 1000 ℃;
Preferably, the described roasting time of step (2) is at least 4 hours, more preferably 5 ~ 40 hours, is particularly preferably 6 ~ 32 hours.
8. such as each described method of claim 3-7, it is characterized in that, the described roasting of step (2) is carried out under oxidizing atmosphere, particularly preferably in carrying out under air and/or the oxygen atmosphere; Preferably, the flow of described oxidizing atmosphere is 2 ~ 150mL/min, and more preferably 3 ~ 120mL/min is particularly preferably 5 ~ 100mL/min;
Preferably, cool off after the described roasting of step (2) is finished; Preferably, described being cooled to naturally cools to room temperature;
Preferably, pulverizing after the described roasting of step (2) is finished, classification, screening obtain heterogeneous manganese based solid solution.
9. such as each described method of claim 3-8, it is characterized in that the described Combined Mining spray drying process of step (3);
Preferably, described spray drying process comprises: the suspension-turbid liquid of heterogeneous manganese based solid solution material slowly is added in the graphene dispersing solution, mixes, spray drying obtains heterogeneous manganese based solid solution composite positive pole;
Preferably, the suspension-turbid liquid of described heterogeneous manganese based solid solution material contains surfactant;
Preferably, the solvent of the suspension-turbid liquid of described heterogeneous manganese based solid solution material is water;
Preferably, described surfactant be that stearic acid, neopelex, fatty glyceride, amino acid, lecithin, aliphatic acid sorb are smooth, a kind or at least 2 kinds combination in polysorbate, polyoxyethylene and the polyoxypropylene;
Preferably, the mass ratio of described surfactant and heterogeneous manganese based solid solution material is 0.05:100 ~ 10:100, is particularly preferably 0.08:100 ~ 8:100, is particularly preferably 0.1:100～5:100;
Preferably, the solvent of described graphene dispersing solution is a kind or at least 2 kinds combination in water, ethanol, methyl alcohol, glycerine, acetone, oxolane, benzene or the toluene.
10. such as each described method of claim 3-9, it is characterized in that, said method comprising the steps of:
(1) with Li source compound, manganese source compound, nickel source compound and cobalt source compound, join successively in the aqueous solution of dispersant, be stirred to the formation suspension-turbid liquid, suspension-turbid liquid ground with the rotating speed of 100 ~ 800r/min made slurry at least in 1 hour, adopt spray dryer that described slurry is carried out spray drying, make and contain manganese, nickel, the equally distributed spheroidization presoma of three kinds of metallic elements of cobalt;
(2) the spheroidization presoma that step (1) is obtained places sintering furnace, with the following programming rate of 20 ℃/min, be warmed up in 600 ~ 1100 ℃ of scopes, be incubated at least 4 hours, in roasting process, pass into continuously simultaneously oxidizing atmosphere, flow velocity is 2 ~ 150mL/min, naturally cools to room temperature after the roasting, and obtains heterogeneous manganese based solid solution through pulverizing, classification, screening;
(3) under agitation, the heterogeneous manganese based solid solution material adding that step (2) is obtained contains in the aqueous solution of surfactant, form suspension-turbid liquid, slowly join suspension-turbid liquid in the graphene dispersing solution, fully stir and form heterogeneous manganese based solid solution/Graphene mixed slurry, adopt spray dryer that mixed slurry is carried out spray drying, obtain heterogeneous manganese based solid solution composite positive pole.
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