CN103500831A - Manganese-based solid solution positive electrode material doped with anions and preparation method thereof - Google Patents
Manganese-based solid solution positive electrode material doped with anions and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a manganese-based solid solution positive electrode material doped with anions. The structural general formula of the manganese-based solid solution positive electrode material is that Li[Li((x+1)/(2+x))Mn(x/(2+x))M((1-x)/(x+2))]O2-mY2m/z, wherein the Y is moping anions, the M is transition metal layer doping elements, 0<x<1 and 0<m<0.2, the z is the valence of the moping anions Y, one or more of S2-, PO43-, SiO44-, BO33- and SO42- are preferably used in the Y, and the transition metal layer doping elements M are generally selected from one or more anions of Co, Ni, Fe and Cr. The doping elements are added into the manganese-based solid solution material, a more stable chemical bond is formed with O so that the position of the O in the crystal structure can be stabilized, the stability of the crystal structure is obviously improved, and therefore better electrochemical stability can be achieved.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries and preparation method field, be specifically related to anion doped manganese based solid solution positive electrode and preparation method thereof.
Background technology
Chemical power source is the key link of current great new energy technology development, and lithium ion battery, as the highest chemical energy storage system of energy density in current chemical power source, at mobile phone, has been obtained great success in the portable type electronic product markets such as notebook.Yet commercial lithium ion battery is due to its positive electrode LiCoO instantly
2lower (the about 140mAhg of actual specific capacity
-1), expensive, the factor such as poisonous, restricted it further at following electric automobile, the application of the great new forms of energy application such as energy-accumulating power station.Therefore, develop the study hotspot that anode material for lithium-ion batteries of future generation becomes new energy field.Wherein, manganese based solid solution material (surpasses 250mAhg because specific capacity is high
-1), with low cost, environmental friendliness has been subject to researchers' extensive concern.
Although manganese based solid solution material in the literature widespread reports higher specific capacity, but because its electronic conductance is on the low side, caused its high rate performance poor, and the capacity attenuation in cyclic process is very fast, these factors have stoped the further large-scale application of manganese based solid solution material.A kind of mode of improving under study for action this manganese based solid solution material property is ion doping.In manganese based solid solution material, the O ion forms the framework of crystal by hexagonal closs packing, cation (Co, Ni, Mn etc.) be filled among the space of the framework that cation forms, form the hexagonal layered structure, the stability of O ion in lattice has very important impact to crystal framework stable.Laboratory, U.S. Argonne has been reported and has been mixed F manganese based solid solution material Li (Li
0.2ni
0.15+0.5zco
0.10mn
0.55 0.5z) O
2 zf
zchemical property, the F doping is to substitute the position of O ion in lattice, because transition-metal cation M and F have stronger bonding action, so can stable crystal structure, improve cycle performance, although the electrode material capacity after F processes decreases, electrochemical stability and the thermal stability of this material are improved, and show material application prospect preferably.On the other hand, the doping principle of F ion is that the F doping is to substitute the position of O ion in lattice, and F-O is without the chemical bonding effect, and this doping way is limited to the raising of structural stability.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of anion doped manganese based solid solution positive electrode and preparation method thereof for above-mentioned prior art, the purpose of material electrochemical stability, to build more firm crystal framework, is realized improving in position (O in non-replacement lattice) by O in the firm lattice of anion doped element.
The present invention addresses the above problem adopted technical scheme: a kind of anion doped manganese based solid solution positive electrode, its general structure is Li[Li
((x+1)/(2+x))mn
(x/(2+x))m
((1-x)/(x+2))] O
2-my
2m/z, in formula, Y is the doping anion, M is the transition metal layer doped chemical, and 0<x<1,0<m<0.2, z is the chemical valence of doping anion Y.
Particularly, described doping anion Y is S
2-, PO
4 3-, SiO
4 4-, BO
3 3-, SO
4 2-in one or more, transition metal layer doped chemical M is Co, Ni, Fe, one or more in Cr.
Further with improvement, described doped chemical Y comprises F to such scheme
-and S
2-, PO
4 3-, SiO
4 4-, BO
3 3-, SO
4 2-in one or more.
With S
2-, PO
4 3-, SiO
4 4-, BO
3 3-, SO
4 2-deng joining as doped chemical in manganese based solid solution material structure, form and there is the P-O that more stablizes bond energy, S-O, Si-O, the B-O key, P, S, Si, the B element is to stablize the position of O ion in lattice in lattice, with this, builds more stable crystal framework.
For doped chemical can be incorporated in material equably, the present invention adopts the heat of polymerization solution to prepare anion doped manganese based solid solution positive electrode, and concrete steps are:
1) to LiOHH
2dropwise add acrylic acid or acrylic acid derivative in the O aqueous solution, the mixed solution that adds the slaine of the contained metallic element Mn of transition metal layer, M after mixing, the lithium salts, ammonium salt or the respective acids that add again Y after stirring, make the polymer monomer solution that contains Y, the structure of polymer monomer is CH
2=C (R
1) COOM
1, R in formula
1for H or CH
3, M
1for Li, Mn, M;
2) add initator in the polymer monomer solution that contains Y of step 1, in 60 ~ 100 ℃ of temperature ranges, carry out polymerization reaction, polymer is dried and made polymer precursor;
3) polymer precursor of step 2 carried out to pyrolytic reaction, after compressing tablet again high-temperature calcination obtain target product Li[Li
((x+1)/(2+x))mn
(x/(2+x))m
((1-x)/(x+2))] O
2-my
2m/z, in formula, Y is the doping anion, M is the transition metal layer doped chemical, and 0<x<1,0<m<0.2, z is the chemical valence of doping anion Y.
Preferably, the slaine of the contained metallic element Mn of the transition metal layer of described step 1, M is each metallic element nitrate, acetate or oxalates.
Preferably, the initator of described step 2 is a kind of in hydrogen peroxide, persulfate and sulphite.
Particularly, the temperature of described step 3 pyrolytic reaction is 300 ~ 500 ℃, and the temperature of calcination reaction is 600 ~ 1000 ℃, and calcination time is 6 ~ 15 hours.
Compared with prior art, the invention has the advantages that: adopt anion as S
2-, PO
4 3-, SiO
4 4-, BO
3 3-, SO
4 2-deng joining as doped chemical in manganese based solid solution material structure, form more stable chemical bond to stablize the position of O in crystal structure with O, improve significantly crystal structural stability, thereby obtained better electrochemical stability.Adopt the method for polymerization pyrolysis to prepare doped with manganese based solid solution positive electrode, doped chemical is that the mode of mixing with atom occurs at blend step, thereby mixed fully between doped chemical and material body element, improved the doping effect, and the preparation method is simple and easy to control, be convenient to promote.
The accompanying drawing explanation
Fig. 1 is LMO material and different proportion PO thereof in the embodiment of the present invention 1
4 3-dopant material, first all charging and discharging curve figure under the 30mA/g current density.
Fig. 2 is LMO material and different proportion PO thereof in the embodiment of the present invention 1
4 3-dopant material is 50 weeks cyclic curve figure under the 30mA/g current density.
Fig. 3 is LMO material and PFLMO material 30 weeks cyclic curve figure under the 100mA/g current density in the embodiment of the present invention 2.
Fig. 4 is LMO material and P-B-LMO material 50 weeks cyclic curve figure under the 100mA/g current density in the embodiment of the present invention 3.
LMO material and Si-F-LMO material 50 weeks cyclic curve figure under the 100mA/g current density in Fig. 5 embodiment of the present invention 4.
Embodiment
Below in conjunction with accompanying drawing embodiment, technical scheme of the present invention is described in further detail.
PO
4 3-doped with manganese based solid solution material Li[Li
0.2co
0.13ni
0.13mn
0.54] O
2-3x/2(PO
4)
xthe preparation of (x=1%, 3%, 5%, 10%)
By 18.047g LiOHH
2o is water-soluble, more dropwise adds the 50ml acrylic acid solution, then by the 13.235g Co (NO mixed
3)
2﹒ 6H
2o, 13.212g Ni (NO
3)
2﹒ 6H
2o and 67.618g Mn (NO
3)
2mixed solution adds wherein, after stirring, adds (the NH of corresponding proportion
4) H
2pO
4, finally add the 1ml 5% ammonium persulfate initiator aqueous solution, at 80 ℃ of lower initiated polymerization 2h, then polymer is dried under 120 ℃, obtain polymer precursor.Polymer precursor is at 450 ℃ of lower pyrolysis 5h, and be pressed into disk under 10MPa pressure after, under 900 ℃, calcining 12h obtains target product Li[Li
0.2co
0.13ni
0.13mn
0.54] O
2-3x/2(PO
4)
x(x=1%, 3%, 5%, 10%).
By prepared PO
4 3-doped with manganese based solid solution material Li[Li
0.2co
0.13ni
0.13mn
0.54] O
2-3x/2(PO
4)
x(x=1%, 3%, 5%, 10%) with do not carry out anion doped naked material Li[Li
0.2co
0.13ni
0.13mn
0.54] O
2(after referred to as LMO) is assembled into 2016 type button cells and carries out electro-chemical test, and Fig. 1 is LMO material and different proportion PO thereof
4 3-dopant material, first all charging and discharging curve figure under the 30mA/g current density, show in figure that the first all charge/discharge specific capacities of LMO material are 365/293, it is 346/297 that the first all charge/discharge specific capacities of different proportion dopant material are followed successively by, 335/286,330/256,272/222.Fig. 2 is LMO material and different proportion PO thereof
4 3-dopant material, 50 weeks cyclic curve figure under the 30mA/g current density, in figure, result shows that 50 weeks capability retentions of LMO material are 80%, 50 weeks capability retentions of different proportion dopant material are followed successively by 85.5%, 91.5%, 92%, 96.8%, PO
4 3-after doping, the electrochemical stability of material is significantly improved.
Embodiment 2
F
-and PO
4 3-doped with manganese based solid solution material Li[Li
0.2co
0.13ni
0.13mn
0.54] O
1.98(PO
4)
0.01f
0.01preparation
By 18.547g LiOHH
2o, LiF is water-soluble, more dropwise adds the 50ml acrylic acid solution, then will close uniform 13.235g Co (NO
3)
2﹒ 6H
2o, 13.212g Ni (NO
3)
2﹒ 6H
2o and 67.618g Mn (NO
3)
2mixed solution adds wherein, after stirring, adds (the NH of corresponding proportion
4) H
2pO
4, finally add the 1ml 5% ammonium persulfate initiator aqueous solution, at 100 ℃ of lower initiated polymerization 2h, then polymer is dried under 120 ℃, obtain polymer precursor.Polymer precursor is at 500 ℃ of lower pyrolysis 5h, and be pressed into disk under 10MPa pressure after, under 1000 ℃, calcining 6h obtains target product Li[Li
0.2co
0.13ni
0.13mn
0.54] O
1.98(PO
4)
0.01f
0.01
By prepared PO
4 3-doped with manganese based solid solution material Li[Li
0.2co
0.13ni
0.13mn
0.54] O
1.98(PO
4)
0.01f
0.01(being called for short afterwards P-F-LMO) with do not carry out anion doped naked material Li[Li
0.2co
0.13ni
0.13mn
0.54] O
2(after referred to as LMO) is assembled into 2016 type button cells and carries out electro-chemical test, the capacity circulating curve that Fig. 3 is LMOPF material and LMO material, under the 100mA current density, P-F-LMO and LMO electrode can realize 242 respectively, 244mAh/g, after circulation in 30 weeks, the capability retention of P-F-LMO is up to being 93%, and the capability retention of LMO is 84%.
PO
4 3-, BO
3 3-codope manganese based solid solution material Li[Li
0.2co
0.13ni
0.13mn
0.54] O
1.97(BO
3)
0.01(PO
4)
0.01preparation
By 18.547g LiOHH
2o is water-soluble, more dropwise adds the 50ml acrylic acid solution, then will close uniform 13.235g Co (NO
3)
2﹒ 6H
2o, 13.212g Ni (NO
3)
2﹒ 6H
2o and 67.618g Mn (NO
3)
2mixed solution adds wherein, after stirring, adds (the NH of corresponding proportion
4) H
2pO
4, NH
4b
5o
84H
2o, finally add 1ml 5% ammonium sulfite initiator solution, at 60 ℃ of lower initiated polymerization 2h, then polymer dried under 120 ℃, obtains polymer precursor.Polymer precursor is at 300 ℃ of lower pyrolysis 5h, and be pressed into disk under 10MPa pressure after, under 600 ℃, calcining 15h obtains marking product Li[Li
0.2co
0.13ni
0.13mn
0.54] O
1.97(BO
3)
0.01(PO
4)
0.01.
By prepared PO
4 3-, BO
3 3-codope manganese based solid solution material Li[Li
0.2co
0.13ni
0.13mn
0.54] O
1.97(BO
3)
0.01(PO
4)
0.01(being called for short afterwards P-B-LMO) material Li[Li naked with it
0.2co
0.13ni
0.13mn
0.54] O
2(after referred to as LMO) is assembled into 2016 type button cells and carries out electro-chemical test, the capacity circulating curve that Fig. 4 is P-B-LMO and LMO material, under the 100mA current density, P-B-LMO and LMO electrode can realize 218 respectively, 244mAh/g, after circulation in 50 weeks, the capability retention of P-B-LMO is up to being 97.9%, and the capability retention of LMO is 82%.
Embodiment 4
SiO
4 4-, F
-codope manganese based solid solution Li[Li
0.2co
0.13ni
0.13mn
0.54] O
1.975(SiO
4)
0.01f
0.01preparation
By 18.547g LiOHH
2o, LiF is water-soluble, more dropwise adds the 50ml acrylic acid solution, then by the 13.235g Co (NO mixed
3)
2﹒ 6H
2o, 13.212g Ni (NO
3)
2﹒ 6H
2o and 67.618g Mn (NO
3)
2mixed solution adds wherein, after stirring, adds (the NH of corresponding proportion
4)
4siO
4, finally add 1ml hydrogen peroxide initator, at 80 ℃ of lower initiated polymerization 2h, then polymer is dried under 120 ℃, obtain polymer precursor.Polymer precursor is at 450 ℃ of lower pyrolysis 5h, and be pressed into disk under 10MPa pressure after, under 900 ℃, calcining 12h obtains marking product Li[Li
0.2co
0.13ni
0.13mn
0.54] O
1.975(SiO
4)
0.01f
0.01.
By prepared PO
4 3-doped with manganese based solid solution material Li[Li
0.2co
0.13ni
0.13mn
0.54] O
1.975(SiO
4)
0.01f
0.01(being called for short afterwards Si-F-LMO) material Li[Li naked with it
0.2co
0.13ni
0.13mn
0.54] O
2(after referred to as LMO) is assembled into 2016 type button cells and carries out electro-chemical test, the capacity circulating curve that Fig. 5 is Si-F-LMO material and LMO material.Under the 100mA current density, Si-F-LMO and LMO can realize 220,244mAh/g respectively, and through the circulation of 50 weeks, the capability retention of Si-F-LMO was up to being 94%, and the capability retention of LMO is 82%.
Claims (7)
1. an anion doped manganese based solid solution positive electrode, its general structure is Li[Li
((x+1)/(2+x))mn
(x/(2+x))m
((1-x)/(x+2))] O
2-my
2m/z, in formula, Y is the doping anion, M is the transition metal layer doped chemical, and 0<x<1,0<m<0.2, z is the chemical valence of doping anion Y.
2. anion doped manganese based solid solution positive electrode according to claim 1, it is characterized in that: described doping anion Y is S
2-, PO
4 3-, SiO
4 4-, BO
3 3-, SO
4 2-in one or more, transition metal layer doped chemical M is Co, Ni, Fe, one or more in Cr.
3. anion doped manganese based solid solution positive electrode according to claim 2, it is characterized in that: described doping anion Y comprises F
-and S
2-, PO
4 3-, SiO
4 4-, BO
3 3-, SO
4 2-in one or more.
4. a method for preparing anion doped manganese based solid solution positive electrode claimed in claim 1, is characterized in that: comprise the steps:
1) to LiOHH
2dropwise add acrylic acid or acrylic acid derivative in the O aqueous solution, the mixed solution that adds the slaine of the contained metallic element Mn of transition metal layer and M after mixing, the lithium salts, ammonium salt or the respective acids that add again doping anion Y after stirring, make the polymer monomer solution that contains Y, the structure of polymer monomer is CH
2=C (R
1) COOM
1, R in formula
1for H or CH
3, M
1for Li, Mn, M;
2) add initator in the polymer monomer solution that contains Y of step 1, in 60 ~ 100 ℃ of temperature ranges, carry out polymerization reaction, polymer is dried and made polymer precursor;
3) polymer precursor of step 2 carried out to pyrolytic reaction, after compressing tablet again high-temperature calcination obtain target product Li[Li
((x+1)/(2+x))mn
(x/(2+x))m
((1-x)/(x+2))] O
2-my
2m/z, in formula, Y is the doping anion, M is the transition metal layer doped chemical, and 0<x<1,0<m<0.2, z is the chemical valence of doping anion Y.
5. preparation method according to claim 4, is characterized in that: nitrate, acetate or oxalates that the slaine of the contained metallic element Mn of the transition metal layer of described step 1, M is each metallic element.
6. preparation method according to claim 4 is characterized in that: the initator of described step 2 is a kind of in hydrogen peroxide, persulfate and sulphite.
7. preparation method according to claim 4, it is characterized in that: the temperature of described step 3 pyrolytic reaction is 300 ~ 500 ℃, and the temperature of calcination reaction is 600 ~ 1000 ℃, and calcination time is 6 ~ 15 hours.
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