CN103050683B - 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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- CN103050683B CN103050683B CN201210584392.1A CN201210584392A CN103050683B CN 103050683 B CN103050683 B CN 103050683B CN 201210584392 A CN201210584392 A CN 201210584392A CN 103050683 B CN103050683 B CN 103050683B
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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 field of lithium ion battery anode, particularly, the present invention relates to a kind of polyphase manganese base solid solution composite cathode material and preparation method thereof.
Background technology
High-energy-density and high-specific-power are the necessity of future market to lithium ion battery, and the anode material for lithium-ion batteries developing 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 at below 200mAh/g, its energy density is limited.And lithium-rich anode material particularly lithium-rich manganese-based anode material pay close attention to widely because the specific capacity of superelevation and cheaper price cause, the lithium-rich manganese-based anode material mainly stratified material Li of report at present
2mnO
3and LiMO
2(M=Ni, Co, Mn) solid solution that formed, this solid solution specific discharge capacity up to 250mAh/g(theoretical discharge specific capacity at more than 300mAh/g), can meet the demand of following electric automobile power battery to high-energy-density, be one of the most potential current anode material for lithium-ion batteries.
Although rich lithium manganese base solid solution material has significant advantage, but consider from practical angle, still there is many difficult problems urgently to be resolved hurrily: (1) initial coulomb efficiency low (generally only 60 ~ 70%), cause the negative material demand matched to increase, be difficult to the target realizing reducing battery weight and cost of manufacture; (2) native electronic conductivity is not good, causes the high rate performance of material poor, is difficult to the requirement meeting electrokinetic cell; (3) intrinsic ionic conductivity is poor, and cause the cryogenic property of material poor, the scope of application is restricted.
CN102751483A discloses a kind of lithium ion battery stratiform rich lithium manganese base solid solution method for preparing anode material.The employing of this positive electrode is heat-treated presoma and prepared by the method for cooling processing, and its chemical formula is: xLi
2mnO
3(1-x) LiMn
0.4ni
0.4co
0.2o
2(x=0.1 ~ 1.0).Material prepared by the method has higher specific discharge capacity and good cyclical stability, but its high rate performance under big current is poor, time 1C(200mA/g), specific discharge capacity is only about 160mAh/g, and first charge-discharge coulombic efficiency is lower, this cannot meet the requirement of electrical equipment needs fast charging and discharging.
Based on this, the present invention proposes a kind of lithium ion battery polyphase manganese base solid solution composite cathode material and preparation method thereof.
Summary of the invention
Low, the multiplying power of initial coulomb efficiency existed for manganese based solid solution material in prior art and the problem of poor performance at low temperatures, an object of the present invention there are provided a kind of capacity and high, the multiplying power of efficiency and the good lithium ion battery polyphase manganese base solid solution composite cathode material of cryogenic property first, has by introducing the spinelle LiMn enriching three-dimensional net structure
1.5-xni
0.5-xco
2xo
4the even Graphene thin layer of phase and high conductivity, significantly improves native electronic conductivity and the ionic conductivity of solid-solution material, efficiently solves an above-mentioned difficult problem.
Described polyphase manganese base solid solution composite cathode material 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.
Described heterogeneous manganese based solid solution contains 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 the three-dimensional net structure spinelle LiMn that space group is Fd3m
1.5-xni
0.5-xco
2xo
4three-phase.Li
2mnO
3there is rock-steady structure and storage lithium performance, LiMn
0.5-xni
0.5-xco
2xo
2there is high power capacity, LiMn
1.5-xni
0.5-xco
2xo
4there is 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, wherein 0≤x < 0.5, 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, more preferably 0.08:100 ~ 15:100,0.1:100 ~ 10:100.
An object of the present invention there are provided a kind of preparation method of described polyphase manganese base solid solution composite cathode material.The preparation method of described polyphase manganese base solid solution composite cathode material is on the basis that drying process with atomizing prepares the equal phase precursor of spheroidization, by control Li/M(M=Mn, Ni, Co) molar ratio and Mn, Ni, Co molar ratio sintering prepare and have 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 the three-dimensional net structure spinelle LiMn that space group is 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 obtain.
The preparation method of described polyphase manganese base solid solution composite cathode material, comprises the following steps:
(1) Li source compound, manganese source compound, nickel source compound and cobalt source compound are mixed, dry, obtain spheroidization presoma;
(2) the spheroidization presoma that step (1) obtains is carried out roasting, obtain heterogeneous manganese based solid solution;
(3) in the heterogeneous manganese based solid solution surface recombination graphene layer that step (2) obtains, polyphase manganese base solid solution composite cathode material is obtained.
It will be understood by those skilled in the art that x=0(is not namely containing cobalt in the general formula of described heterogeneous manganese based solid solution) time, step (1) does not add cobalt source compound.
Preferably, step (1) described mixing comprises: be added to by raw material in dispersant solution, ball milling; Preferably, described dispersant solution is aqueous dispersant; Preferably, described ball milling adopts roller ball grinding jar; Preferably, described ball milling speed is 100 ~ 800r/min, more preferably 150 ~ 600r/min, is particularly preferably 200 ~ 500r/min; Preferably, described Ball-milling Time is at least 1h, more preferably 1.5 ~ 40h, is particularly preferably 2 ~ 30h; Preferably, described dispersant is the combination of in butadiene-styrene rubber (SBR), polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC) a kind or at least 2 kinds; 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, step (1) described drying is spraying dry.
Preferably, described Li source compound is lithium chloride, lithium bromide, lithium phosphate, phosphoric acid hydrogen two lithium, lithium dihydrogen phosphate, lithium sulfate, lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate, lithium oxalate, lithium formate, tert-butyl alcohol lithium, 1 kind in lithium benzoate and lithium citrate or the combination of at least 2 kinds, 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 lithium 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 lithium, the combination etc. of lithium sulfate and lithium hydroxide, be particularly preferably the combination of in lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate, lithium oxalate, lithium formate, tert-butyl alcohol lithium, lithium benzoate and lithium citrate a kind or at least 2 kinds.
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 in manganese dioxide and hydroxyl oxidize manganese or the combination of at least 2 kinds, 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 etc. of manganese sesquioxide managnic oxide and manganese dioxide, be particularly preferably the combination of in manganese nitrate, manganese acetate, manganese oxalate, manganese carbonate, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese dioxide and hydroxyl oxidize manganese a kind or at least 2 kinds.
Preferably, described nickel source compound is, 1 kind in nickel phosphate, nickel hydroxide, nickel nitrate, nickel acetate, nickel oxalate, nickelous carbonate and nickel oxide or the combination of at least 2 kinds, 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 etc. of nickel phosphate, nickel hydroxide, nickel nitrate, nickel acetate and nickel oxalate; Be particularly preferably the combination of in nickel nitrate, nickel acetate, nickel oxalate, nickelous carbonate, nickel oxide and nickel hydroxide a kind or at least 2 kinds.
Preferably, described cobalt source compound is the combination of in cobalt nitrate, cobalt acetate, cobalt oxalate, cobalt carbonate, cobaltosic oxide and cobalt hydroxide a kind or at least 2 kinds, 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 etc. of cobalt acetate, cobalt oxalate, cobalt carbonate, cobaltosic oxide and cobalt hydroxide.
Preferably, the described roasting of step (2) adopts sintering furnace.
Preferably, the programming rate of step (2) described roasting is 20 DEG C/below min, such as 0.1 DEG C/min, 0.2 DEG C/min, 0.5 DEG C/min, 0.8 DEG C/min, 0.9 DEG C/min, 1.1 DEG C/min, 1.5 DEG C/min, 1.9 DEG C/min, 2.1 DEG C/min, 2.2 DEG C/min, 2.5 DEG C/min, 3 DEG C/min, 5 DEG C/min, 8 DEG C/min, 9 DEG C/min, 11 DEG C/min, 13 DEG C/min, 14 DEG C/min, 16 DEG C/min, 18 DEG C/min, 19 DEG C/min, 21 DEG C/min, 25 DEG C/min etc., more preferably 1 ~ 15 DEG C/min, is particularly preferably 2 ~ 10 DEG C/min.
Preferably, step (2) described sintering temperature is 600 ~ 1100 DEG C, more preferably 700 ~ 1050 DEG C, is particularly preferably 750 ~ 1000 DEG C.
Preferably, step (2) described roasting time 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, step (2) described roasting is carried out in an oxidizing atmosphere, carries out particularly preferably under air and/or oxygen atmosphere; Preferably, the flow of described oxidizing atmosphere is 2 ~ 150mL/min, more preferably 3 ~ 120mL/min, is particularly preferably 5 ~ 100mL/min.
Preferably, step (2) described roasting cools after completing; Preferably, be cooled to described in and naturally cool to room temperature.
Preferably, step (2) described roasting complete after pulverizing, 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: be slowly added in graphene dispersing solution by the suspension-turbid liquid of heterogeneous manganese based solid solution material, mixing, and spraying dry, obtains polyphase manganese base solid solution composite cathode material; 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 the combination of in stearic acid, neopelex, fatty glyceride, amino acid, lecithin, aliphatic acid sorb smooth (sapn), polysorbate (Tween-60), polyoxyethylene and polyoxypropylene a kind or at least 2 kinds; 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 the combination of in water, ethanol, methyl alcohol, glycerine, acetone, oxolane, benzene or toluene a kind or at least 2 kinds; The typical but non-limiting preparation method of described graphene dispersing solution can comprise: take a certain amount of Graphene and join in appropriate solvent, ultrasonic 20 ~ 100min, electric stirring 2 ~ 10h, is mixed with graphene dispersing solution.
The preparation method of described polyphase manganese base solid solution composite cathode material, comprises the following steps:
(1) by Li source compound, manganese source compound, nickel source compound and cobalt source compound, join successively in the aqueous solution of dispersant, be stirred to formation suspension-turbid liquid, by suspension-turbid liquid with the rotating speed of 100 ~ 800r/min grinding at least 1 hour obtained slurry, spray dryer is adopted to carry out spraying dry to described slurry, obtained manganese, nickel, the equally distributed spheroidization presoma of cobalt three kinds of metallic elements;
(2) the spheroidization presoma that step (1) obtains is placed in sintering furnace, with the programming rate of 20 DEG C/below min, be warmed up within the scope of 600 ~ 1100 DEG C, be incubated at least 4 hours, in roasting process, pass into oxidizing atmosphere continuously simultaneously, flow velocity is 2 ~ 150mL/min, naturally cools to room temperature after roasting, and obtains heterogeneous manganese based solid solution through pulverizing, classification, screening;
(3) under agitation, heterogeneous manganese based solid solution material step (2) obtained adds in the aqueous solution containing surfactant, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in graphene dispersing solution, abundant stirring forms heterogeneous manganese based solid solution/Graphene mixed slurry, adopt spray dryer to carry out spraying dry to mixed slurry, obtain polyphase manganese base solid solution composite cathode material.
By the method for the invention, there is 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 the three-dimensional net structure spinelle LiMn that space group is Fd3m
1.5-xni
0.5-xco
2xo
4three-phase forms solid solution, greatly accelerates Li
+embedding and deviate from speed, significantly improve the intrinsic ionic conductivity of solid solution, the initial coulomb efficiency of solid solution and cryogenic property be improved significantly; Form uniform graphene layer by spraying dry on solid solution surface simultaneously, and adopt surfactant to make between solid solution and Graphene, to have good adhesion, greatly reduce interface contact resistance between the two, improve the native 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 polyphase manganese base solid solution composite cathode material 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, wherein 0≤x < 0.5, a:b:c is (0 ~ 0.5): (0.1 ~ 0.7): (0.1 ~ 0.7), and 0 < a≤0.5, a+b+c=1, except having the Li in conventional Mn-based material
2mnO
3and LiMO
2(M=Ni, Co, Mn) mutually outside, also by control Li/M(M=Mn, Ni, Co) molar ratio and Mn, Ni, Co molar ratio introduce the LiMn that space group is Fd3m
1.5-xni
0.5-xco
2xo
4phase, this crystalline phase, owing to having abundant three-dimensional network spinel structure, accelerates Li greatly
+embedding and deviate from speed, significantly improve the intrinsic ionic conductivity of solid solution, the initial coulomb efficiency of solid solution and cryogenic property be improved significantly;
(2) the present invention is on the basis of the heterogeneous manganese based solid solution of preparation, by spray-dired mode, achieve evenly coated on solid solution surface of Graphene, simultaneously owing to adding surfactant in spray process, make that there is between solid solution and Graphene good adhesion, greatly reduce interface contact resistance between the two, improve the native electronic conductivity of solid-solution material, the high rate performance of heterogeneous manganese based solid solution composite material is significantly improved;
(3) to have initial coulomb efficiency high for polyphase manganese base solid solution composite cathode material of the present invention, good with negative material matching, energy density is high, and the advantage such as the good and high rate performance of Stability Analysis of Structures is superior under high voltage charge and discharge condition, specific discharge capacity is up to 268mAh/g, higher by 60% than the capacity of cobalt acid lithium and LiFePO4, first charge-discharge efficiency reaches 85%, and has good matching with hard carbon and silicon-carbon class high-capacity cathode material; Under 2C multiplying power, specific discharge capacity still reaches 190mAh/g, and high rate performance significantly improves; Under-20 DEG C of cryogenic conditions, capability retention is more than 70%.
Accompanying drawing explanation
Fig. 1 is the SEM figure of presoma prepared by the embodiment of the present invention 2.
Fig. 2 (a) is the profile of presoma prepared by the embodiment of the present invention 2; Fig. 2 (b) is the mapping of nickel element in the presoma of the embodiment of the present invention 2 preparation; Fig. 2 (c) is the mapping of cobalt element in the presoma of the embodiment of the present invention 2 preparation; Fig. 2 (d) is the mapping of manganese element in the presoma of the embodiment of the present invention 2 preparation.
Fig. 3 (a) is the XRD collection of illustrative plates of the positive electrode of the embodiment of the present invention 2, comparative example 1 and comparative example 2 preparation; Wherein, a is positive electrode prepared by embodiment 2, and b is positive electrode prepared by comparative example 1, and c is positive electrode prepared by comparative example 2.
Fig. 4 is the FE-SEM figure of raw materials used Graphene in the embodiment of the present invention.
Fig. 5 (a) is the FE-SEM figure of composite positive pole prepared by the embodiment of the present invention 2; Fig. 5 (b) is the FE-SEM figure of positive electrode prepared by comparative example 2.
Fig. 6 is the charging and discharging curve figure of the positive electrode of the embodiment of the present invention 2, comparative example 1 and comparative example 2 preparation; Wherein, a is positive electrode prepared by embodiment 2, and b is positive electrode prepared by comparative example 1, and c is positive electrode prepared by comparative example 2.
Fig. 7 is the high rate performance curve chart of the embodiment of the present invention 1 ~ 7 and comparative example 1 ~ 2, and wherein, a, b, c, d, e, f and g respectively are positive electrode prepared by embodiment 1 ~ 7; H and i is respectively the positive electrode of comparative example 1 and comparative example 2 preparation.
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 is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
By lithium hydroxide 14mo1, manganese nitrate 7mol, nickel nitrate 2mo1, cobalt nitrate 1mo1 Homogeneous phase mixing is also dispersed in cmc soln, is stirred to formation suspension-turbid liquid; Suspension-turbid liquid is transferred in roller ball grinding jar, obtains viscous paste with the rotating speed of 400r/min grinding 5h; Spray dryer is adopted to carry out spraying dry to above-mentioned slurry, obtained manganese, nickel, the equally distributed spherical presoma of cobalt three kinds of metallic elements; Presoma is placed in sintering furnace, with the programming rate of 5 DEG C/min, be warmed up to 950 DEG C, insulation 10h, dry air is passed into continuously in roasting process, flow velocity is 20mL/min, naturally cools to room temperature after 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
2; Be that 2:100 takes a certain amount of Graphene and joins in 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 containing being in the Tween-60 aqueous solution of 0.2:100 with the mass ratio of heterogeneous manganese based solid solution material, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in graphene dispersing solution, fully stirs and form heterogeneous manganese based solid solution/Graphene mixed slurry; Adopt spray dryer to carry out spraying dry to mixed slurry, 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
By lithium hydroxide 13.2mo1, manganese nitrate 7mol, nickel nitrate 2mol, cobalt nitrate 1mo1 Homogeneous phase mixing is also dispersed in the PVA aqueous solution, is stirred to formation suspension-turbid liquid; Suspension-turbid liquid is transferred in roller ball grinding jar, obtains viscous paste with the rotating speed of 400r/min grinding 5h; Spray dryer is adopted to carry out spraying dry to above-mentioned slurry, obtained manganese, nickel, the equally distributed spherical presoma of cobalt three kinds of metallic elements; Presoma is placed in sintering furnace, with the programming rate of 5 DEG C/min, be warmed up to 950 DEG C, insulation 10h, in roasting process, pass into dry air continuously simultaneously, flow velocity is 20mL/min, naturally cools to room temperature after 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.Be that 2:100 takes a certain amount of Graphene and joins in 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 containing being in the Tween-60 aqueous solution of 0.2:100 with the mass ratio of heterogeneous manganese based solid solution material, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in graphene dispersing solution, fully stirs and form heterogeneous manganese based solid solution/Graphene mixed slurry; Spray dryer is adopted to carry out spraying dry to mixed slurry, obtained 0.1LiMn
1.4ni
0.4co
0.2o
40.45Li
2mnO
30.45LiMn
0.4ni
0.4co
0.2o
2composite positive pole.
Embodiment 3
By lithium hydroxide 11.7mo1, manganese nitrate 7mol, nickel nitrate 2mo1, cobalt nitrate 1mo1 Homogeneous phase mixing is also dispersed in cmc soln, is stirred to formation suspension-turbid liquid.Suspension-turbid liquid is transferred in roller ball grinding jar, obtains viscous paste with the rotating speed of 400r/min grinding 5h.Spray dryer is adopted to carry out spraying dry to above-mentioned slurry, obtained manganese, nickel, the equally distributed spherical presoma of cobalt three kinds of metallic elements, presoma is put in sintering furnace, with the programming rate of 5 DEG C/min, be warmed up to 950 DEG C, insulation 10h, in roasting process, pass into dry air continuously simultaneously, flow velocity is 20mL/min, naturally cools to room temperature after 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
2.Be that 5:100 takes a certain amount of Graphene and joins in 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 containing being in the aqueous solution of the Tween-60 of 0.2:100 with the mass ratio of heterogeneous manganese based solid solution material, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in graphene dispersing solution, fully stirs and form heterogeneous manganese based solid solution/Graphene mixed slurry.Spray dryer is adopted to carry out spraying dry to slurry, obtained 0.2LiMn
1.4ni
0.4co
0.2o
40.4Li
2mnO
30.4LiMn
0.4ni
0.4co
0.2o
2composite positive pole.
Embodiment 4
By lithium nitrate 13.2mo1, manganese acetate 6.5mol, nickel acetate 1.5mo1, cobalt acetate 2.0mo1 Homogeneous phase mixing is also dispersed in the PVA aqueous solution, is stirred to formation suspension-turbid liquid, obtains viscous paste with the rotating speed of 400r/min grinding 5h.Spray dryer is adopted to carry out spraying dry to above-mentioned slurry, obtained manganese, nickel, the equally distributed spherical presoma of cobalt three kinds of metallic elements.Presoma is put in sintering furnace, with the programming rate of 5 DEG C/min, be warmed up to 950 DEG C, insulation 10h, in roasting process, pass into dry air continuously simultaneously, flow velocity is 20mL/min, naturally cools to room temperature after 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
2.Be that 10:100 takes a certain amount of Graphene and joins in 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 containing being in the aqueous solution of the Tween-60 of 0.2:100 with the mass ratio of heterogeneous manganese based solid solution material, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in graphene dispersing solution, fully stirs and form heterogeneous manganese based solid solution/Graphene mixed slurry; Spray dryer is adopted to carry out spraying dry to slurry, obtained 0.1LiMn
1.3ni
0.3co
0.4o
40.45Li
2mnO
30.45LiMn
0.3ni
0.3co
0.4o
2composite positive pole.
Embodiment 5
By lithium acetate 13.2mo1, manganese acetate 6.67mol, nickel acetate 1.65mo1, cobalt acetate 1.65mo1 Homogeneous phase mixing is also dispersed in cmc soln, is stirred to formation suspension-turbid liquid.Suspension-turbid liquid is transferred in roller ball grinding jar, obtains viscous paste with the rotating speed of 400r/min grinding 5h.Spray dryer is adopted to carry out spraying dry to above-mentioned slurry, obtained manganese, nickel, the equally distributed spherical presoma of cobalt three kinds of metallic elements.Presoma is put in sintering furnace, with the programming rate of 5 DEG C/min, be warmed up to 950 DEG C, insulation 10h, in roasting process, pass into dry air continuously simultaneously, flow velocity is 20mL/min, naturally cools to room temperature after 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
2.Be that 2:100 takes a certain amount of Graphene and joins in 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 containing being in the aqueous solution of the Tween-60 of 0.2:100 with the mass ratio of heterogeneous manganese based solid solution material, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in graphene dispersing solution, fully stirs and form heterogeneous manganese based solid solution/Graphene mixed slurry.Spray dryer is adopted to carry out spraying dry to mixed slurry, obtained 0.1LiMn
1.33ni
0.33co
0.333o
40.45Li
2mnO
30.45LiMn
0.333ni
0.333co
0.333o
2composite positive pole.
Embodiment 6
By lithium acetate 13.2mo1, manganese acetate 7.25mol, nickel acetate 2.25mo1, cobalt acetate 0.50mo1 Homogeneous phase mixing is also dispersed in PVA solution, is stirred to formation suspension-turbid liquid.Suspension-turbid liquid is transferred in roller ball grinding jar, obtains viscous paste with the rotating speed of 400r/min grinding 5h.Spray dryer is adopted to carry out spraying dry to above-mentioned slurry, obtained manganese, nickel, the equally distributed spherical presoma of cobalt three kinds of metallic elements.Presoma is put in sintering furnace, with the programming rate of 5 DEG C/min, be warmed up to 950 DEG C, insulation 10h, in roasting process, pass into dry air continuously simultaneously, flow velocity is 20mL/min, naturally cools to room temperature after 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
2.Be that 0.1:100 takes a certain amount of Graphene and joins in 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 containing being in the aqueous solution of the Tween-60 of 0.1:100 with the mass ratio of heterogeneous manganese based solid solution material, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in graphene dispersing solution, abundant stirring forms heterogeneous manganese based solid solution/Graphene mixed slurry, spray dryer is adopted to carry out spraying dry to slurry, obtained 0.1LiMn
1.45ni
0.45co
0.1o
40.45Li
2mnO
30.45LiMn
0.45ni
0.45co
0.1o
2composite positive pole.
Embodiment 7
By lithium acetate 13.2mo1, manganese acetate 7.5mol, nickel acetate 2.5mo1 Homogeneous phase mixing is also dispersed in cmc soln, is stirred to formation suspension-turbid liquid.Suspension-turbid liquid is transferred in roller ball grinding jar, obtains viscous paste with the rotating speed of 400r/min grinding 5h.Spray dryer is adopted to carry out spraying dry to above-mentioned slurry, obtained manganese, the equally distributed spherical presoma of nickel two kinds of metallic elements, presoma is put in sintering furnace, with the programming rate of 5 DEG C/min, be warmed up to 950 DEG C, insulation 10h, in roasting process, pass into dry air continuously simultaneously, flow velocity is 20mL/min, naturally cools to room temperature after 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
2.Be that 10:100 takes a certain amount of Graphene and joins in 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 containing being in the aqueous solution of the Tween-60 of 5:100 with the mass ratio of heterogeneous manganese based solid solution material, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in graphene dispersing solution, fully stirs and form heterogeneous manganese based solid solution/Graphene mixed slurry.Spray dryer is adopted to carry out spraying dry to slurry, obtained 0.3LiMn
1.5ni
0.5o
40.2Li
2mnO
30.5LiMn
0.5ni
0.5o
2composite positive pole.
Embodiment 8
By lithium oxalate 11mo1, mangano-manganic oxide 6.09mol, nickel hydroxide 0.09mo1, cobalt hydroxide 8.82mo1 Homogeneous phase mixing is also dispersed in PVA solution, is stirred to formation suspension-turbid liquid.Suspension-turbid liquid is transferred in roller ball grinding jar, obtains viscous paste with the rotating speed of 800r/min grinding 1h.Spray dryer is adopted to carry out spraying dry to above-mentioned slurry, obtained manganese, nickel, the equally distributed spherical presoma of cobalt three kinds of metallic elements.Presoma is put in sintering furnace, with the programming rate of 20 DEG C/min, be warmed up to 1100 DEG C, insulation 4h, in roasting process, pass into dry air continuously simultaneously, flow velocity is 150mL/min, naturally cools to room temperature after 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
2.Be that 0.05:100 takes a certain amount of Graphene and joins in 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 containing being in the aqueous solution of the lecithin of 0.05:100 with the mass ratio of heterogeneous manganese based solid solution material, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in graphene dispersing solution, abundant stirring forms heterogeneous manganese based solid solution/Graphene mixed slurry, spray dryer is adopted to carry out spraying dry to slurry, obtained 0.5LiMn
1.01ni
0.01co
0.98o
40.1Li
2mnO
30.4LiMn
0.01ni
0.01co
0.98o
2composite positive pole.
Embodiment 9
By phosphoric acid hydrogen two lithium 12.9mo1, manganous hydroxide 6.479mol, nickel oxide 3.479mo1, cobalt oxalate 0.142mo1 Homogeneous phase mixing is also dispersed in cmc soln, is stirred to formation suspension-turbid liquid; Suspension-turbid liquid is transferred in roller ball grinding jar, obtains viscous paste with the rotating speed of 100r/min grinding 15h; Spray dryer is adopted to carry out spraying dry to above-mentioned slurry, obtained manganese, nickel, the equally distributed spherical presoma of cobalt three kinds of metallic elements; Presoma is placed in sintering furnace, with the programming rate of 1 DEG C/min, be warmed up to 600 DEG C, insulation 40h, dry air is passed into continuously in roasting process, flow velocity is 2mL/min, naturally cools to room temperature after 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
2; Be that 20:100 takes a certain amount of Graphene and joins in 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 containing being in the aqueous solution of the neopelex of 10:100 with the mass ratio of heterogeneous manganese based solid solution material, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in graphene dispersing solution, fully stirs and form heterogeneous manganese based solid solution/Graphene mixed slurry; Adopt spray dryer to carry out spraying dry to mixed slurry, obtain 0.01LiMn
1.49ni
0.49co
0.02o
40.29Li
2mnO
30.7LiMn
0.49ni
0.49co
0.02o
2composite positive pole.
Embodiment 10
By lithium chloride 17mo1, manganese carbonate 9.3mol, nickel phosphate 0.3mo1, cobaltosic oxide 2.4mo1 Homogeneous phase mixing is also dispersed in cmc soln, is stirred to formation suspension-turbid liquid.Suspension-turbid liquid is transferred in roller ball grinding jar, obtains viscous paste with the rotating speed of 150r/min grinding 10h.Spray dryer is adopted to carry out spraying dry to above-mentioned slurry, obtained manganese, nickel, the equally distributed spherical presoma of cobalt three kinds of metallic elements, presoma is put in sintering furnace, with the programming rate of 15 DEG C/min, be warmed up to 1050 DEG C, insulation 5h, in roasting process, pass into dry air continuously simultaneously, flow velocity is 3mL/min, naturally cools to room temperature after 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
2.Be that 15:100 takes a certain amount of Graphene and joins in 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 containing being in the aqueous solution of the polyoxypropylene of 0.07:100 with the mass ratio of heterogeneous manganese based solid solution material, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in graphene dispersing solution, fully stirs and form heterogeneous manganese based solid solution/Graphene mixed slurry.Spray dryer is adopted to carry out spraying dry to slurry, obtained 0.2LiMn
1.1ni
0.1co
0.8o
40.7Li
2mnO
30.1LiMn
0.1ni
0.1co
0.8o
2composite positive pole.
Comparative example 1
By lithium hydroxide 15mo1, manganese nitrate 7mol, nickel nitrate 2mo1, cobalt nitrate 1mo1 Homogeneous phase mixing is also dispersed in cmc soln, is stirred to formation suspension-turbid liquid; Suspension-turbid liquid is transferred in roller ball grinding jar, obtains viscous paste with the rotating speed of 400r/min grinding 5h.Adopt spray dryer to carry out spraying dry to above-mentioned slurry, the inlet temperature of spray dryer is 250 DEG C, and outlet temperature is 120 DEG C, and charging rate is 20mL/min, by obtained manganese of spraying, nickel, the equally distributed spherical presoma of cobalt three kinds of metallic elements.Presoma is put in sintering furnace, with the programming rate of 5 DEG C/min, be warmed up to 950 DEG C, insulation 10h, in roasting process, pass into dry air continuously simultaneously, flow velocity is 20mL/min, naturally cools to room temperature after 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 example 2
By lithium hydroxide 13.2mo1, manganese nitrate 7mol, nickel nitrate 2mo1, cobalt nitrate 1mo1 Homogeneous phase mixing is also dispersed in cmc soln, is stirred to formation suspension-turbid liquid.Suspension-turbid liquid is transferred in roller ball grinding jar, obtains viscous paste with the rotating speed of 400r/min grinding 5h; Adopt spray dryer to carry out spraying dry to above-mentioned slurry, the inlet temperature of spray dryer is 250 DEG C, and outlet temperature is 120 DEG C, and charging rate is 20mL/min, by obtained manganese of spraying, nickel, the equally distributed spherical presoma of cobalt three kinds of metallic elements.Presoma is placed in sintering furnace, with the programming rate of 5 DEG C/min, be warmed up to 950 DEG C, insulation 10h, dry air is passed into continuously in roasting process, flow velocity is 20mL/min, naturally cools to room temperature after 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 example 1 ~ 2 obtain is tested.
Fig. 1 is the SEM figure of the presoma in the embodiment of the present invention 2.As shown in Figure 1, presoma even particle size distribution, and in good spherical morphology.
Fig. 2 is profile and Ni, Co, Mn mapping of presoma in the embodiment of the present invention 2.As shown in Figure 2, manganese, nickel and manganese element, in the distribution of spheric granules inner homogeneous, illustrate that presoma prepared by drying process with atomizing can the molecule rank Homogeneous phase mixing of realization response raw material.
Fig. 3 is the XRD collection of illustrative plates of the embodiment of the present invention 2, comparative example 1 and comparative example 2.As shown in Figure 3, the 0.5Li of preparation in comparative example 1
2mnO
30.5LiMn
0.4ni
0.4co
0.2o
2material contains the monocline stratiform Li that space group is C2/m
2mnO
3with the rocking chair stratiform LiMn that space group is R-3m
0.5-xni
0.5-xco
2xo
2the characteristic diffraction peak of two crystalline phases.By contrast, the 0.1LiMn of comparative example 2 preparation
1.4ni
0.4co
0.2o
40.45Li
2mnO
30.45LiMn
0.4ni
0.4co
0.2o
2material is three-phase solid solution material, and it is except having the characteristic diffraction peak of material in comparative example 1, have also appeared the three-dimensional net structure high-voltage spinel LiMn that space group is Fd3m
1.5-xni
0.5-xco
2xo
4the characteristic peak of phase.Compared with comparative example 2,0.1LiMn prepared by embodiment 2
1.4ni
0.4co
0.2o
40.45Li
2mnO
30.45LiMn
0.4ni
0.4co
0.2o
2except having the characteristic diffraction peak of three solid solution phases, there is the characteristic diffraction peak of graphite at about 25 ° in composite positive pole simultaneously.
Fig. 4 is the FE-SEM figure of raw materials used Graphene in the embodiment of the present invention.As seen from the figure, the present invention's grapheme material used has multi-layer nano sheet-like morphology, and structure is preserved comparatively complete.
Fig. 5 is the SEM figure of the embodiment of the present invention 2 and comparative example 2.Contrast two figure can find out, before Graphene of not spraying, the surface of primary particle is comparatively smooth, and after spraying Graphene step, particle surface becomes coarse, at Surface coating one deck uniform flake graphite alkene material of heterogeneous manganese based solid solution.
Fig. 6 is the charging and discharging curve figure of the embodiment of the present invention 2, comparative example 1 and comparative example 2.As can be seen from the figure, the 0.1LiMn in 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 efficiency reaches 85.7% first, is obviously better than in comparative example 1 and does not mix high-voltage spinel LiMn
1.4ni
0.4co
0.2o
4mutually with the 0.5Li not carrying out graphene coated process
2mnO
30.5LiMn
0.4ni
0.4co
0.2o
2graphene coated process 0.1LiMn is not carried out in positive electrode and comparative example 2
1.4ni
0.4co
0.2o
40.45Li
2mnO
30.45LiMn
0.4ni
0.4co
0.2o
2positive electrode, illustrates thus through introducing high-voltage spinel LiMn
1.4ni
0.4co
0.2o
4mutually and after carrying out the coated process of graphenic surface, the specific discharge capacity of composite material has had raising to a certain degree, and first charge-discharge efficiency then significantly improves.
Fig. 7 is the high rate performance curve chart of the embodiment of the present invention 1 ~ 7, comparative example 1 ~ 2.As can be seen from the figure, through introducing high-voltage spinel LiMn
1.4ni
0.4co
0.2o
4mutually and after carrying out the coated process of graphenic surface, the high rate performance of composite material is significantly improved.
Table 1 is the simulated battery test result of embodiment 1 ~ 9 and comparative example 1 ~ 2.
Table 1
Contrast as can be seen from table 1, through introducing high-voltage spinel LiMn
1.4ni
0.4co
0.2o
4phase, material capability retention under low temperature (-20 DEG C) obtains obvious improvement, brings up to 60.2% in comparative example 2 by 35.4% in comparative example 1, and after graphene coated process, and material capability retention has at low temperatures been got back further raising.In addition, it can also be seen that from table, after graphene coated process, the material circulation stability in embodiment is significantly improved, and after 50 weeks charge and discharge cycles, the capacity of material has brought up to about 95% by 80% time not coated.
Applicant states, 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, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (37)
1. a polyphase manganese base solid solution composite cathode material, comprises heterogeneous manganese based solid solution and Graphene, and wherein, 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, wherein 0≤x < 0.5, a:b:c is (0 ~ 0.5): (0.1 ~ 0.7): (0.1 ~ 0.7), and 0 < a≤0.5, a+b+c=1; The mass ratio that described Graphene accounts for heterogeneous manganese based solid solution is 0.05:100 ~ 20:100.
2. polyphase manganese base solid solution composite cathode material as claimed in claim 1, it is characterized in that, 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.
3. polyphase manganese base solid solution composite cathode material as claimed in claim 2, it is characterized in that, 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.
4. polyphase manganese base solid solution composite cathode material as claimed in claim 1, it is characterized in that, the mass ratio that described Graphene accounts for heterogeneous manganese based solid solution is 0.08:100 ~ 15:100.
5. a preparation method for polyphase manganese base solid solution composite cathode material as claimed in claim 1, comprises the following steps:
(1) Li source compound, manganese source compound, nickel source compound and cobalt source compound are mixed, dry, obtain spheroidization presoma;
(2) the spheroidization presoma that step (1) obtains is carried out roasting, obtain heterogeneous manganese based solid solution;
(3) in the heterogeneous manganese based solid solution surface recombination graphene layer that step (2) obtains, polyphase manganese base solid solution composite cathode material is obtained.
6. method as claimed in claim 5, it is characterized in that, step (1) described mixing comprises: be added to by raw material in dispersant solution, ball milling.
7. method as claimed in claim 6, it is characterized in that, described dispersant solution is aqueous dispersant.
8. method as claimed in claim 6, is characterized in that, described ball milling adopts roller ball grinding jar.
9. method as claimed in claim 6, it is characterized in that, described ball milling speed is 100 ~ 800r/min.
10. method as claimed in claim 6, is characterized in that, described Ball-milling Time is at least 1h.
11. methods as claimed in claim 6, is characterized in that, described dispersant is the combination of in butadiene-styrene rubber, polyvinyl alcohol, carboxymethyl cellulose a kind or at least 2 kinds.
12. methods as claimed in claim 6, is characterized in that, described dispersant is 0.05 ~ 4% of described heterogeneous manganese based solid solution gross mass.
13. methods as claimed in claim 5, it is characterized in that, step (1) described drying is spraying dry.
14. methods as claimed in claim 5, it is characterized in that, described Li source compound is the combination of in lithium chloride, lithium bromide, lithium phosphate, phosphoric acid hydrogen two lithium, lithium dihydrogen phosphate, lithium sulfate, lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate, lithium oxalate, lithium formate, tert-butyl alcohol lithium, lithium benzoate and lithium citrate a kind or at least 2 kinds.
15. methods as claimed in claim 5, it is characterized in that, described manganese source compound is the combination of in manganese phosphate, manganous hydroxide, manganese nitrate, manganese acetate, manganese oxalate, manganese carbonate, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese dioxide and hydroxyl oxidize manganese a kind or at least 2 kinds.
16. methods as claimed in claim 15, is characterized in that, described manganese source compound is the combination of in manganese nitrate, manganese acetate, manganese oxalate, manganese carbonate, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese dioxide and hydroxyl oxidize manganese a kind or at least 2 kinds.
17. methods as claimed in claim 5, is characterized in that, described nickel source compound is the combination of in nickel phosphate, nickel hydroxide, nickel nitrate, nickel acetate, nickel oxalate, nickelous carbonate and nickel oxide a kind or at least 2 kinds.
18. methods as claimed in claim 17, is characterized in that, described nickel source compound is the combination of in nickel nitrate, nickel acetate, nickel oxalate, nickelous carbonate, nickel oxide and nickel hydroxide a kind or at least 2 kinds.
19. methods as claimed in claim 5, is characterized in that, described cobalt source compound is the combination of in cobalt nitrate, cobalt acetate, cobalt oxalate, cobalt carbonate, cobaltosic oxide and cobalt hydroxide a kind or at least 2 kinds.
20. methods as claimed in claim 5, is characterized in that, the described roasting of step (2) adopts sintering furnace.
21. methods as claimed in claim 5, is characterized in that, the programming rate of described roasting is 20 DEG C/below min.
22. methods as claimed in claim 5, it is characterized in that, described sintering temperature is 600 ~ 1100 DEG C.
23. methods as claimed in claim 5, it is characterized in that, described roasting time is at least 4 hours.
24. methods as claimed in claim 5, it is characterized in that, step (2) described roasting is carried out in an oxidizing atmosphere.
25. methods as claimed in claim 24, is characterized in that, the flow of described oxidizing atmosphere is 2 ~ 150mL/min.
26. methods as claimed in claim 24, it is characterized in that, described roasting is carried out under air and/or oxygen atmosphere.
27. methods as claimed in claim 5, is characterized in that, cool after step (2) described roasting completes.
28. methods as claimed in claim 27, is characterized in that, described in be cooled to and naturally cool to room temperature.
29. methods as claimed in claim 5, is characterized in that, pulverizing after step (2) described roasting completes, classification, screening obtain heterogeneous manganese based solid solution.
30. methods as claimed in claim 5, is characterized in that, the described Combined Mining spray drying process of step (3).
31. methods as claimed in claim 30, it is characterized in that, described spray drying process comprises: be slowly added in graphene dispersing solution by the suspension-turbid liquid of heterogeneous manganese based solid solution material, and mixing, spraying dry, obtains polyphase manganese base solid solution composite cathode material.
32. methods as claimed in claim 31, is characterized in that, the suspension-turbid liquid of described heterogeneous manganese based solid solution material contains surfactant.
33. methods as claimed in claim 32, is characterized in that, the solvent of the suspension-turbid liquid of described heterogeneous manganese based solid solution material is water.
34. methods as claimed in claim 32, it is characterized in that, described surfactant is that stearic acid, neopelex, fatty glyceride, amino acid, lecithin, aliphatic acid sorb are smooth, the combination of in polysorbate, polyoxyethylene and polyoxypropylene a kind or at least 2 kinds.
35. methods as claimed in claim 32, is characterized in that, the mass ratio of described surfactant and heterogeneous manganese based solid solution material is 0.05:100 ~ 10:100.
36. methods as claimed in claim 31, is characterized in that, the solvent of described graphene dispersing solution is the combination of in water, ethanol, methyl alcohol, glycerine, acetone, oxolane, benzene or toluene a kind or at least 2 kinds.
37. methods as claimed in claim 5, is characterized in that, said method comprising the steps of:
(1) by Li source compound, manganese source compound, nickel source compound and cobalt source compound, join successively in the aqueous solution of dispersant, be stirred to formation suspension-turbid liquid, by suspension-turbid liquid with the rotating speed of 100 ~ 800r/min grinding at least 1 hour obtained slurry, spray dryer is adopted to carry out spraying dry to described slurry, obtained containing manganese, nickel, the equally distributed spheroidization presoma of cobalt three kinds of metallic elements;
(2) the spheroidization presoma that step (1) obtains is placed in sintering furnace, with the programming rate of 20 DEG C/below min, be warmed up within the scope of 600 ~ 1100 DEG C, be incubated at least 4 hours, in roasting process, pass into oxidizing atmosphere continuously simultaneously, flow velocity is 2 ~ 150mL/min, naturally cools to room temperature after roasting, and obtains heterogeneous manganese based solid solution through pulverizing, classification, screening;
(3) under agitation, heterogeneous manganese based solid solution material step (2) obtained adds in the aqueous solution containing surfactant, form suspension-turbid liquid, suspension-turbid liquid is slowly joined in graphene dispersing solution, abundant stirring forms heterogeneous manganese based solid solution/Graphene mixed slurry, adopt spray dryer to carry out spraying dry to mixed slurry, obtain polyphase manganese base solid solution composite cathode material.
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| JP6109399B1 (en) * | 2016-03-31 | 2017-04-05 | Ｂａｓｆ戸田バッテリーマテリアルズ合同会社 | Positive electrode active material particles for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery |
| KR102518143B1 (en) * | 2016-11-04 | 2023-04-05 | 한국전기연구원 | Method of manufacturing the active material using a spray-dried, thereby the active material and energy storage device including the active material |
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| CA2578870C (en) * | 2004-09-03 | 2016-01-26 | The University Of Chicago | Manganese oxide composite electrodes for lithium batteries |
| US7935270B2 (en) * | 2006-10-04 | 2011-05-03 | Samsung Sdi Co., Ltd | Cathode active material and lithium battery using the same |
| CN101752561B (en) * | 2009-12-11 | 2012-08-22 | 宁波艾能锂电材料科技股份有限公司 | Graphite alkene iron lithium phosphate positive active material, preparing method thereof, and lithium ion twice battery based on the graphite alkene modified iron lithium phosphate positive active material |
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