CN105024067A - Lithium ion battery, composite doping modified positive electrode active material thereof and preparation method - Google Patents
Lithium ion battery, composite doping modified positive electrode active material thereof and preparation method Download PDFInfo
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- CN105024067A CN105024067A CN201410160715.3A CN201410160715A CN105024067A CN 105024067 A CN105024067 A CN 105024067A CN 201410160715 A CN201410160715 A CN 201410160715A CN 105024067 A CN105024067 A CN 105024067A
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Abstract
The invention provides a lithium ion battery, a composite doping modified positive electrode active material thereof and a preparation method. The general formula of the composite doping modified positive electrode active material is LirQ<1-x>MxVO<4-y>Ny, wherein M and N are doping elements; Q is one of Co, Ni, Mn, Cr, Al, Mg, Fe and Cu; M is at least one of Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, Zr, La, Ti, Ca, Ba, B and Si; N is at least one of F, Cl, Br, I, olivine polyanions and acid radicals; r is more than 0.6 and is not more than 1.05; x is more than 0 and is not more than 0.25; y is more than 0 and is not more than 0.30; Q and M are not the same; an X-ray diffraction (XRD) pattern of the composite doping modified positive electrode active material comprises a strongest diffraction peak (311) and characteristic peaks of inverse spinel, namely a weak peak (111) and a moderately strong peak (220). The lithium ion battery comprises the composite doping modified positive electrode active material. The composite doping modified positive electrode active material has a stable structure and good morphology. The first discharge operating voltage platform, the first specific discharge capacity, the first coulombic efficiency and the capacity retention ratio after multiple cycles of the lithium ion battery are higher.
Description
Technical field
The present invention relates to field of batteries, particularly relate to a kind of lithium ion battery and composite doping modification positive electrode active materials thereof and preparation method.
Background technology
Lithium ion battery has the advantages such as operating voltage is high, specific energy is large, security performance is good, be widely used in the portable such as mobile communication, notebook computer electronic product, along with its application in pure electric vehicle, hybrid electric vehicle and large-scale energy storage field, people are to the performance of lithium ion battery, and especially energy density and multiplying power density are had higher requirement.The energy density of lithium ion battery is relevant with specific capacity with the operating voltage of lithium ion battery, and the positive electrode active materials therefore seeking high voltage and jumbo lithium ion battery has very important significance.
The positive electrode active materials of the lithium ion battery of current use, as LiCoO
2, LiMn
2o
4, LiFePO
4, LiNi
xco
ymn
1-x-yo
2operating voltage all lower than 4V, the energy density of lithium ion battery and multiplying power density are restricted in application.Lithium-barium oxide because of its high power capacity, low cost (price of vanadium comparatively cobalt, manganese is low), pollution-free, reserves are many etc., and advantage becomes one of positive electrode active materials of the rising lithium ion battery of most.Because vanadium has multivalence, therefore VO can be formed
2, V
2o
5, V
6o
13, V
4o
9and V
3o
7etc. multiple barium oxide, these barium oxides can form stratiform lithium intercalation compound, and can form again spinel-type lithium intercalation compound and inverse spinel structure lithium intercalation compound, specific capacity reaches as high as 334mAh/g.
In recent years, inverse spinel structure lithium-barium oxide causes people and pays close attention to greatly, and in this compound, lithium atom is in the space of octahedral coordination, and vanadium atom is in the space of tetrahedral coordination.Compared with the lithium-barium oxide of other type, the cation degree of mixing of inverse spinel structure lithium-barium oxide can reach 100%, and discharge voltage wants high a lot (LiNiVO
44.8V can be reached, LiCoVO
44.2V can be reached), the specific capacity of inverse spinel structure lithium-barium oxide can reach 148mAh/g in theory, but the specific capacity of reality is lower, and its specific capacity along with the increase attenuation ratio of cycle-index very fast, so await exploring its structure further, find better preparation method and effective modified method improves its chemical property.Summary of the invention
In view of Problems existing in background technology, the object of the present invention is to provide a kind of lithium ion battery and composite doping modification positive electrode active materials thereof and preparation method, the Stability Analysis of Structures of described composite doping modification positive electrode active materials, pattern are good, and the working voltage platform of discharging first of described lithium ion battery, first discharge specific capacity, first coulombic efficiency and the capability retention repeatedly after circulation are all higher.
In order to realize foregoing invention object, in a first aspect of the present invention, the invention provides a kind of composite doping modification positive electrode active materials, its general formula is Li
rq
1-xm
xvO
4-yn
ywherein, M, N are doped chemical, Q is the one in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, and M is at least one in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, Zr, La, Ti, Ca, Ba, B, Si, and N is at least one in F, Cl, Br, I, olivine-type polyanion, acid group, 0.6<r≤1.05,0<x≤0.25,0 < y≤0.30, and Q with M is not identical; Li
rq
1-xm
xvO
4-yn
yfor space group Fd-3m (O
h 7), Li atom is in the space of octahedral coordination, and V atom is in the space of tetrahedral coordination, Li atom, position shared by metallic atom Q and doped chemical M are (16d, 1/2,1/2,1/2), the position shared by V atom is (8a, 1/4,1/4,1/4), O atom and the position shared by doped chemical N are (32e, x, x, x); The XRD diffracting spectrum of described composite doping modification positive electrode active materials comprises the characteristic peak of the strongest diffraction maximum (311) and inverse spinel: weak peak (111) and time strong peak (220).
In a second aspect of the present invention, the invention provides a kind of preparation method of composite doping modification positive electrode active materials, for the preparation of composite doping modification positive electrode active materials according to a first aspect of the present invention, comprise step: part is dissolved in deionized water by (1), form ligand solution; (2) Li salt, Q salt, M salt, V salt, N salt are dissolved in deionized water, form uniform mixed solution, wherein, Q is the one in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, M is at least one in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, Zr, La, Ti, Ca, Ba, B, Si, N is at least one in F, Cl, Br, I, olivine-type polyanion, acid group, and Q with M is not identical; (3) mixed solution of step (2) gained is slowly joined in the ligand solution of step (1) gained, and under agitation form emulsion; (4) by the emulsion of step (3) gained heating water bath at 60 DEG C ~ 100 DEG C, transpiring moisture, and constantly stir, obtain wet gel; (5) by the vacuumize at 100 DEG C ~ 150 DEG C of the wet gel of step (4) gained, xerogel is obtained; (6) by the pre-burning at 400 DEG C ~ 600 DEG C of the xerogel of step (5) gained, precursor is obtained; (7) precursor of step (6) gained is naturally cooled to room temperature, make base substrate at grinding in ball grinder powdered afterwards; (8) base substrate of step (7) gained is calcined at 600 DEG C ~ 1200 DEG C, naturally cool to after room temperature at grinding in ball grinder powdered; (9) by the tempering at 100 DEG C ~ 400 DEG C of the powder of step (8) gained, obtain composite doping modification positive electrode active materials, the general formula of described composite doping modification positive electrode active materials is Li
rq
1-xm
xvO
4-yn
y, wherein, 0.6<r≤1.05,0<x≤0.25,0 < y≤0.30; Li
rq
1-xm
xvO
4-yn
yfor space group Fd-3m (O
h 7), Li atom is in the space of octahedral coordination, and V atom is in the space of tetrahedral coordination, Li atom, position shared by metallic atom Q and doped chemical M are (16d, 1/2,1/2,1/2), the position shared by V atom is (8a, 1/4,1/4,1/4), O atom and the position shared by doped chemical N are (32e, x, x, x); The XRD diffracting spectrum of described composite doping modification positive electrode active materials comprises the characteristic peak of the strongest diffraction maximum (311) and inverse spinel: weak peak (111) and time strong peak (220).
In a third aspect of the present invention, the invention provides a kind of lithium ion battery, it comprises: anode pole piece, comprises composite doping modification positive electrode active materials; Cathode pole piece; Barrier film, is interval between anode pole piece and cathode pole piece; And electrolyte.Described composite doping modification positive electrode active materials is composite doping modification positive electrode active materials according to a first aspect of the present invention.
Beneficial effect of the present invention is as follows:
(1) gained of the present invention the single-phase free from admixture of composite doping modification positive electrode active materials, crystal property is good, grain diameter is even, smooth surface.
(2) the present invention passes through to Li
rqVO
4mix the cations such as Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, Zr, La, Ti, Ca, Ba, B, Si in positive electrode active materials and replace Li with part
rqVO
4in metallic atom Q, mix the anion such as F, Cl, Br, I, olivine-type polyanion, acid group with part replace Li
rqVO
4in O atom, the mode of this Anion-cation multiple dope can take into account cationic rock-steady structure, play the cooperative effect of anion simultaneously, make the working voltage platform of discharging first of the lithium ion battery of gained, first discharge specific capacity, first coulombic efficiency and the capability retention after repeatedly circulating all higher.
(3) preparation method of composite doping modification positive electrode active materials of the present invention is easy to operate, and technique is simple, with low cost, easy to implement and carry out suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the composite doping modification positive electrode active materials of the embodiment of the present invention 1 gained.
Fig. 2 is scanning electron microscopy (SEM) image of the composite doping modification positive electrode active materials of the embodiment of the present invention 1 gained.
Fig. 3 is the first charge-discharge curve chart of 2032 type button cells of the embodiment of the present invention 1 gained.
Fig. 4 is that the first charge-discharge specific capacity of 2032 type button cells of the embodiment of the present invention 1 gained is to the differential curve figure of charging/discharging voltage.
Fig. 5 is the comparison diagram of discharge curve first of 2032 type button cells of the embodiment of the present invention 1 and comparative example 1 gained.
Fig. 6 is the cyclic curve comparison diagram of 2032 type button cells stage by stage under different multiplying of the embodiment of the present invention 1 and comparative example 1 gained.
Embodiment
The following detailed description of lithium ion battery according to the present invention and composite doping modification positive electrode active materials thereof and preparation method and embodiment, comparative example and test result.
First composite doping modification positive electrode active materials is according to a first aspect of the present invention described.
Composite doping modification positive electrode active materials according to a first aspect of the present invention, its general formula is Li
rq
1-xm
xvO
4-yn
ywherein, M, N are doped chemical, Q is the one in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, and M is at least one in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, Zr, La, Ti, Ca, Ba, B, Si, and N is at least one in F, Cl, Br, I, olivine-type polyanion, acid group, 0.6<r≤1.05,0<x≤0.25,0 < y≤0.30, and Q with M is not identical; Li
rq
1-xm
xvO
4-yn
yfor space group Fd-3m (O
h 7), Li atom is in the space of octahedral coordination, and V atom is in the space of tetrahedral coordination, Li atom, position shared by metallic atom Q and doped chemical M are (16d, 1/2,1/2,1/2), the position shared by V atom is (8a, 1/4,1/4,1/4), O atom and the position shared by doped chemical N are (32e, x, x, x); The XRD diffracting spectrum of described composite doping modification positive electrode active materials comprises the characteristic peak of the strongest diffraction maximum (311) and inverse spinel: weak peak (111) and time strong peak (220).
At composite doping modification positive electrode active materials Li of the present invention
rq
1-xm
xvO
4-yn
yin, cationic doped chemical M part substituted metal atom Q, the lattice of composite doping modification positive electrode active materials can be made to diminish, and structure tends towards stability, and then improve the chemical property of composite doping modification positive electrode active materials, improve the cycle life of lithium ion battery; And the doped chemical N part of anion replaces O atom, effectively can increase the electron acceptor of composite doping modification positive electrode active materials, make forming section oxygen defect in crystal, the vacancy volume in structure cell increases, thus is conducive to the embedding of lithium ion and deviates from.
The mode of Anion-cation multiple dope can fully utilize the advantage of zwitterion, makes their shortcoming cancel out each other as far as possible simultaneously, and makes it produce cooperative effect to improve the combination property of lithium ion battery.Anion-cation multiple dope not only can improve crystallinity and the tap density of positive electrode active materials, positive electrode active materials chemical property under high pressure can also be improved, and then improve the cycle performance of lithium ion battery, and the initial specific capacities of positive electrode active materials increases, and then the capability retention of lithium ion battery is also higher.
In composite doping modification positive electrode active materials described according to a first aspect of the present invention, described metallic element Q preferably can be the one in Co, Ni, Mn, Cr; Described doped chemical M preferably can be at least one in Cr, Al, Fe, Zr, La; Described doped chemical N preferably can be at least one in F, Cl, Br.Be preferably containing single electron in the electron configuration of the doped chemical M of transition metal, have the valency layer d track of underfill, based on eighteen-electron rule, its character and other yuan have significant difference, can have the valence state ion that plurality of stable exists.And be preferably halogen doped chemical N outermost electron on have 7 electronics, have acquisition 1 electronics to form the tendency of the halogen ion of stable octet structure, thus have stronger electronegativity, chemical property is more active.Therefore the present invention preferably adopts the two (i.e. doped chemical M employing transition metal, doped chemical N is halogen) composite doping modification is carried out to inverse spinel structure positive electrode active materials, under guarantee inverse spinel structure positive electrode active materials lattice and constitutionally stable prerequisite, improve the chemical property of lithium ion battery.
In composite doping modification positive electrode active materials described according to a first aspect of the present invention, preferably, 0.8<r≤1.02,0.01<x≤0.22,0.02<y≤0.25.
In composite doping modification positive electrode active materials described according to a first aspect of the present invention, the charging/discharging voltage scope of described composite doping modification positive electrode active materials can be 2.0V ~ 5.5V, preferably can be 2.5V ~ 5.0V, to ensure that lithium ion can embed completely and deviate from composite doping modification positive electrode active materials in charge and discharge process, and ensure that redox reaction is fully carried out, and then lithium ion battery is made to show excellent chemical property.
Secondly the preparation method of composite doping modification positive electrode active materials is according to a second aspect of the present invention described.
The preparation method of composite doping modification positive electrode active materials according to a second aspect of the present invention, comprises step: part is dissolved in deionized water by (1), forms ligand solution; (2) Li salt, Q salt, M salt, V salt, N salt are dissolved in deionized water, form uniform mixed solution, wherein, Q is the one in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, M is at least one in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, Zr, La, Ti, Ca, Ba, B, Si, N is at least one in F, Cl, Br, I, olivine-type polyanion, acid group, and Q with M is not identical; (3) mixed solution of step (2) gained is slowly joined in the ligand solution of step (1) gained, and under agitation form emulsion; (4) by the emulsion of step (3) gained heating water bath at 60 DEG C ~ 100 DEG C, transpiring moisture, and constantly stir, obtain wet gel; (5) by the vacuumize at 100 DEG C ~ 150 DEG C of the wet gel of step (4) gained, xerogel is obtained; (6) by the pre-burning at 400 DEG C ~ 600 DEG C of the xerogel of step (5) gained, precursor is obtained; (7) precursor of step (6) gained is naturally cooled to room temperature, make base substrate at grinding in ball grinder powdered afterwards; (8) base substrate of step (7) gained is calcined at 600 DEG C ~ 1200 DEG C, naturally cool to after room temperature at grinding in ball grinder powdered; (9) by the tempering at 100 DEG C ~ 400 DEG C of the powder of step (8) gained, obtain composite doping modification positive electrode active materials, the general formula of described composite doping modification positive electrode active materials is Li
rq
1-xm
xvO
4-yn
y, wherein, 0.6<r≤1.05,0<x≤0.25,0 < y≤0.30; Li
rq
1-xm
xvO
4-yn
yfor space group Fd-3m (O
h 7), Li atom is in the space of octahedral coordination, and V atom is in the space of tetrahedral coordination, Li atom, position shared by metallic atom Q and doped chemical M are (16d, 1/2,1/2,1/2), the position shared by V atom is (8a, 1/4,1/4,1/4), O atom and the position shared by doped chemical N are (32e, x, x, x); The XRD diffracting spectrum of described composite doping modification positive electrode active materials comprises the characteristic peak of the strongest diffraction maximum (311) and inverse spinel: weak peak (111) and time strong peak (220).
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (1), described part can be the one in oxalic acid, citric acid, tartaric acid, ethylenediamine tetra-acetic acid, ethylene glycol, acetylacetone,2,4-pentanedione, hydrogen peroxide, preferably can be oxalic acid.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (2), described Li salt can be the one in lithium acetate, lithium nitrate, lithium halide, lithium hydroxide, preferably can be lithium halide.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (2), described Q salt can be the one in the acetate of Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, nitrate, halogen, hydroxide, preferably can be the halogen of Co, Ni, Mn, Cr, Al.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (2), described V salt can be the one in ammonium metavanadate, vanadic oxide, preferably can be ammonium metavanadate.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (2), described M salt can be at least one in the acetate of Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, Zr, La, Ti, Ca, Ba, B, Si, nitrate, halogen, hydroxide, preferably can be the halogen of two kinds of metals in Co, Ni, Mn, Cr, Al, Fe, Zr, La.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (2), described N salt can be at least one in F, Cl, Br, I, olivine-type polyanion, the lithium salts of acid group, sodium salt, sylvite, preferably can be the lithium salts of F, Cl, Br.In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, the mol ratio of the Li ion in the mixed solution that described Li salt, Q salt, M salt, V salt, N salt are formed, Q ion, M ion, V ion, N ion can be 1.02r:(1-x): x:1:y, wherein 0.6<r≤1.05,0<x≤0.25,0<y≤0.30.When cation M doping lower than 0.01 time, it can not replace original Q atom effectively, thus can not form stable lattice; When cation M doping higher than 0.25 time, then too much cation M can be made to enter intracell, occupy the position of Li atom, cause the minimizing of reversible deintercalation Li position, part lattice caves in, and specific discharge capacity declines, and the chemical property of lithium ion battery is deteriorated; When anion N doping lower than 0.01 time, it effectively can not replace original O atom, thus can not form stable lattice; When anion N doping higher than 0.3 time, then can replace original O atom because of too much anion N, cause crystal oxygen defect excessive, the vacancy volumetric expansion in structure cell was lost efficacy, and was unfavorable for the embedding of lithium ion and deviate from.Therefore 0.8<r≤1.02 are preferably, 0.01<x≤0.22,0.02<y≤0.25, the composite doping modification positive electrode active materials adopting preferable range to prepare has more excellent crystal structure and dynamic behavior.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (3), described Li salt, Q salt, M salt, V salt, Li ion in the mixed solution that N salt is formed, Q ion, M ion, the mole sum of V ion can be 1:(1 ~ 3 with the ratio of the mole of part), preferably can be 1:2, effective formation of composite doping modification positive electrode active materials gel and precursor in building-up process can be ensured like this, simultaneously unlikelyly mix the impurity that some later stages not easily remove, and then ensure microscopic appearance and the crystalline structure of composite doping modification positive electrode active materials, thus make lithium ion battery have perfect chemical property.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (4), the time of emulsion heating water bath can be not less than 12h, preferably can be 14h.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (5), the wet gel vacuum drying time can be not less than 5h, preferably can be 6h.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (6), the time of xerogel pre-burning can be not less than 2h, preferably can be 3h.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (7) a metallic, the time of presoma grinding can be 0.5h ~ 2h.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (8), the time of base substrate calcining can be not less than 18h, preferably can be 20h.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (8), the time of base substrate grinding can be 0.5h ~ 2h.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (9), the time of tempering can no longer than 4h.
When treatment temperature and the processing time of each step (step (4) is to step (9)), especially the temperature and time of heating water bath (step (4)) and xerogel pre-burning (step (6)) was not at that time, the specific capacity of composite doping modification positive electrode active materials and the improvement of cycle performance are also not obvious, this may be because doping level is not very perfect, the combination of doped chemical and positive electrode active materials is caused to obtain and built on the sand, under crossing high temperature and crossing long calcining, doped chemical can enter into bulk structure in a large number, the effect of rock-steady structure can not be played, the effect improving crystal structure and chemical property can not be played, and be unfavorable for producing.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (4), the instrument of emulsion heating water bath can be glass surface ware.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (5), the vacuum drying instrument of wet gel can be vacuum drying chamber.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (6), the instrument of xerogel pre-burning can be ceramic crucible.
In the preparation method of composite doping modification positive electrode active materials described according to a second aspect of the present invention, in step (8), the instrument of base substrate calcining can be ceramic crucible.
The selection of suitable heating time, calcination time and instrument, fully carrying out and not causing overreact of synthetic reaction can be ensured, so just, under the prerequisite of purity ensureing synthetic material, the microscopic appearance of synthetic material, crystal structure and chemical property can be ensured further.
Lithium ion battery is according to a third aspect of the present invention described again.
Lithium ion battery according to a third aspect of the present invention, comprising: anode pole piece, comprises composite doping modification positive electrode active materials; Cathode pole piece; Barrier film, is interval between anode pole piece and cathode pole piece; And electrolyte.Described composite doping modification positive electrode active materials is composite doping modification positive electrode active materials according to a first aspect of the present invention.
In lithium ion battery described according to a third aspect of the present invention, described positive conductive agent can be acetylene black; Described positive electrode binder can be polytetrafluoroethylene; Described positive pole dispersant can be absolute ethyl alcohol; Described plus plate current-collecting body can be aluminium foil.
In lithium ion battery described according to a third aspect of the present invention, described cathode pole piece can be metal lithium sheet.
In lithium ion battery described according to a third aspect of the present invention, described barrier film can be Celgard2300.
In lithium ion battery described according to a third aspect of the present invention, the voltage range of described lithium ion battery charge-discharge test can be 2.0V ~ 5.5V, preferably can be 2.5V ~ 5.0V.
Finally illustrate according to the embodiment of lithium ion battery of the present invention and composite doping modification positive electrode active materials and preparation method and comparative example and test process and test result.
Embodiment 1
Composite doping modification positive electrode active materials LiCo
0.97al
0.03vO
3.85f
0.15preparation, it is prepared by following steps:
(1) part ethylene glycol is dissolved in deionized water obtains saturated ethylene glycol ligand solution;
(2) 0.87:0.97:0.03:1:0.15 takes LiNO in molar ratio
3, Co (NO
3)
2, Al (NO
3)
3, NH
4vO
3and LiF be dissolved in deionized water, fully stir and obtain mixed solution;
(3) mixed solution of step (2) gained is slowly joined in the saturated ethylene glycol ligand solution of step (1) gained, and emulsion is obtained under the high-speed stirred of 1200r/min, wherein, the ratio of Li ion, Co ion, Al ion, the mole sum of V ion and the mole of ethylene glycol in the mixed solution of step (2) gained is 1:1;
(4) by the emulsion of step (3) gained heating water bath 12h at 60 DEG C, with transpiring moisture, and constantly stir, obtain wet gel, wherein, mixing speed is 300r/min;
(5) wet gel of step (4) gained is dried 6h in 100 DEG C of vacuum drying chambers, obtain xerogel;
(6) by the xerogel of step (5) gained pre-burning 3h at 400 DEG C, presoma is obtained;
(7) presoma of step (6) gained is naturally cooled to room temperature, afterwards at grinding in ball grinder 0.5 ~ 2h, become powder and make base substrate;
(8) base substrate of step (7) gained is calcined 18h at 600 DEG C, naturally cool to room temperature afterwards, and then grind 1.5h on ball mill, become powder;
(9) by the powder of step (8) gained tempering 1h at 100 DEG C, composite doping modification positive electrode active materials LiCo is namely obtained
0.97al
0.03vO
3.85f
0.15.
Embodiment 2
Composite doping modification positive electrode active materials LiCo
0.93cr
0.07vO
3.90f
0.10preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (1), take oxalic acid as part;
In step (2), 0.92:0.93:0.07:1:0.10 takes LiOH, Co (NO in molar ratio
3)
2, Cr (NO
3)
3, NH
4vO
3and LiF;
In step (3), the ratio of Li ion, Co ion, Cr ion, the mole sum of V ion and the mole of oxalic acid in the mixed solution of step (2) gained is 1:2;
In step (4), the temperature of heating water bath is 70 DEG C;
In step (5), vacuum drying temperature is 120 DEG C;
In step (6), the temperature of pre-burning is 450 DEG C;
In step (8), the temperature of calcining is 800 DEG C.
Embodiment 3
Composite doping modification positive electrode active materials LiCo
0.85fe
0.15vO
3.92cl
0.08preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (1), take acetylacetone,2,4-pentanedione as part;
In step (2), 0.94:0.85:0.15:1:0.08 takes CH in molar ratio
3cOOLi, Co (CH
3cOO)
2, Fe (NO
3)
3, NH
4vO
3and LiCl;
In step (3), the ratio of Li ion, Co ion, Fe ion, the mole sum of V ion and the mole of acetylacetone,2,4-pentanedione in the mixed solution of step (2) gained is 1:3;
In step (4), the temperature of heating water bath is 80 DEG C;
In step (5), vacuum drying temperature is 130 DEG C;
In step (6), the temperature of pre-burning is 500 DEG C;
In step (8), the temperature of calcining is 1000 DEG C;
In step (9), tempering 2h at 200 DEG C.
Embodiment 4
Composite doping modification positive electrode active materials LiCo
0.80la
0.20vO
3.80cl
0.20preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (1), take hydrogen peroxide as part;
In step (2), 0.82:0.80:0.20:1.0:0.20 takes LiNO in molar ratio
3, Co (CH
3cOO)
2, LaCl
3, NH
4vO
3and LiCl;
In step (3), the ratio of Li ion, Co ion, La ion, the mole sum of V ion and the mole of hydrogen peroxide in the mixed solution of step (2) gained is 1:3;
In step (4), the temperature of heating water bath is 100 DEG C;
In step (5), vacuum drying temperature is 150 DEG C;
In step (6), the temperature of pre-burning is 600 DEG C;
In step (8), the temperature of calcining is 1200 DEG C;
In step (9), tempering 2h at 200 DEG C.
Embodiment 5
Composite doping modification positive electrode active materials LiCr
0.85mg
0.15vO
3.96br
0.04preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (2), 0.98:0.85:0.15:1.0:0.04 takes LiNO in molar ratio
3, Cr (CH
3cOO)
3, MgCl
2, NH
4vO
3and LiBr;
In step (3), the ratio of Li ion, Cr ion, Mg ion, the mole sum of V ion and the mole of ethylene glycol in the mixed solution of step (2) gained is 1:1;
In step (9), tempering 2h at 200 DEG C.
Embodiment 6
Composite doping modification positive electrode active materials LiCr
0.95co
0.05vO
3.94br
0.06preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (1), take oxalic acid as part;
In step (2), 0.96:0.95:0.05:1.0:0.06 takes LiNO in molar ratio
3, Cr (CH
3cOO)
3, CoCl
2, NH
4vO
3and LiBr;
In step (3), the ratio of Li ion, Cr ion, Co ion, the mole sum of V ion and the mole of oxalic acid in the mixed solution of step (2) gained is 1:2;
In step (4), the temperature of heating water bath is 70 DEG C;
In step (5), vacuum drying temperature is 120 DEG C;
In step (6), the temperature of pre-burning is 450 DEG C;
In step (8), the temperature of calcining is 800 DEG C;
In step (9), tempering 2h at 200 DEG C.
Embodiment 7
Composite doping modification positive electrode active materials LiCr
0.94zr
0.06vO
3.92i
0.08preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (1), take acetylacetone,2,4-pentanedione as part;
In step (2), 0.94:0.94:0.06:1.0:0.08 takes LiNO in molar ratio
3, CrCl
3, Zr (CH
3cOO)
4, NH
4vO
3and LiI;
In step (3), the ratio of Li ion, Cr ion, Zr ion, the mole sum of V ion and the mole of acetylacetone,2,4-pentanedione in the mixed solution of step (2) gained is 1:3;
In step (4), the temperature of heating water bath is 80 DEG C;
In step (5), vacuum drying temperature is 130 DEG C;
In step (6), the temperature of pre-burning is 500 DEG C;
In step (8), the temperature of calcining is 1000 DEG C;
In step (9), tempering 3h at 400 DEG C.
Embodiment 8
Composite doping modification positive electrode active materials LiCr
0.82cu
0.18vO
3.84i
0.16preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (1), take hydrogen peroxide as part;
In step (2), 0.86:0.82:0.18:1.0:0.16 takes CH in molar ratio
3cOOLi, CrCl
3, Cu (NO
3)
2, NH
4vO
3and LiI;
In step (3), the ratio of Li ion, Cr ion, Cu ion, the mole sum of V ion and the mole of hydrogen peroxide in the mixed solution of step (2) gained is 1:3;
In step (4), the temperature of heating water bath is 100 DEG C;
In step (5), vacuum drying temperature is 150 DEG C;
In step (6), the temperature of pre-burning is 600 DEG C;
In step (8), the temperature of calcining is 1200 DEG C;
In step (9), tempering 3h at 400 DEG C.
Embodiment 9
Composite doping modification positive electrode active materials LiNi
0.86al
0.10cu
0.04vO
3.90f
0.10preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (2), 0.92:0.86:0.10:0.04:0.5:0.10 takes CH in molar ratio
3cOOLi, Ni (OH)
2, Al (NO
3)
3, Cu (NO
3)
2, V
2o
5and LiF;
In step (3), the ratio of Li ion, Ni ion, Al ion, Cu ion, the mole sum of V ion and the mole of ethylene glycol in the mixed solution of step (2) gained is 1:1;
Embodiment 10
Composite doping modification positive electrode active materials LiNi
0.96cr
0.02la
0.02vO
3.98f
0.02preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (1), take oxalic acid as part;
In step (2), 1.0:0.96:0.02:0.02:0.5:0.02 takes LiCl, NiCl in molar ratio
2, Cr (NO
3)
2, La (NO
3)
3, V
2o
5and LiF;
In step (3), the ratio of Li ion, Ni ion, Cr ion, La ion, the mole sum of V ion and the mole of oxalic acid in the mixed solution of step (2) gained is 1:2;
In step (4), the temperature of heating water bath is 70 DEG C;
In step (5), vacuum drying temperature is 120 DEG C;
In step (6), the temperature of pre-burning is 450 DEG C;
In step (8), the temperature of calcining is 800 DEG C.
Embodiment 11
Composite doping modification positive electrode active materials LiNi
0.94zr
0.04fe
0.02vO
3.96cl
0.04preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (1), take acetylacetone,2,4-pentanedione as part;
In step (2), 0.49:0.94:0.04:0.02:0.5:0.04 takes Li in molar ratio
2cO
3, NiCl
2, Zr (NO
3)
4, Fe (NO
3)
3, V
2o
5and LiCl;
In step (3), the ratio of Li ion, Ni ion, Zr ion, Fe ion, the mole sum of V ion and the mole of acetylacetone,2,4-pentanedione in the mixed solution of step (2) gained is 1:3;
In step (4), the temperature of heating water bath is 80 DEG C;
In step (5), vacuum drying temperature is 130 DEG C;
In step (6), the temperature of pre-burning is 500 DEG C;
In step (8), the temperature of calcining is 1000 DEG C;
In step (9), tempering 2h at 200 DEG C.
Embodiment 12
Composite doping modification positive electrode active materials LiNi
0.90fe
0.06la
0.04vO
3.94cl
.006preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (1), take hydrogen peroxide as part;
In step (2), 0.48:0.90:0.06:0.04:0.5:0.06 takes Li in molar ratio
2cO
3, Ni (OH)
2, Fe (NO
3)
3, La (NO
3)
3, V
2o
5and LiCl;
In step (3), the ratio of Li ion, Ni ion, Fe ion, La ion, the mole sum of V ion and the mole of hydrogen peroxide in the mixed solution of step (2) gained is 1:3;
In step (4), the temperature of heating water bath is 100 DEG C;
In step (5), vacuum drying temperature is 150 DEG C;
In step (6), the temperature of pre-burning is 600 DEG C;
In step (8), the temperature of calcining is 1200 DEG C;
In step (9), tempering 2h at 200 DEG C.
Embodiment 13
Composite doping modification positive electrode active materials LiMn
0.88al
0.07co
0.05vO
3.90br
0.10preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (2), 0.92:0.88:0.07:0.05:1.0:0.10 takes LiOH, MnCl in molar ratio
2, Al (NO
3)
3, Co (NO
3)
3, NH
4vO
3and LiBr;
In step (3), the ratio of Li ion, Mn ion, Al ion, Co ion, the mole sum of V ion and the mole of ethylene glycol in the mixed solution of step (2) gained is 1:1;
In step (9), tempering 2h at 200 DEG C.
Embodiment 14
Composite doping modification positive electrode active materials LiMn
0.86cr
0.08cu
0.06vO
3.88br
0.12preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (1), take oxalic acid as part;
In step (2), 0.9:0.86:0.08:0.06:1.0:0.12 takes LiOH, MnCl in molar ratio
2, Cr (NO
3)
3, Cu (NO
3)
2, NH
4vO
3and LiBr;
In step (3), the ratio of Li ion, Mn ion, Cr ion, Cu ion, the mole sum of V ion and the mole of oxalic acid in the mixed solution of step (2) gained is 1:2;
In step (4), the temperature of heating water bath is 70 DEG C;
In step (5), vacuum drying temperature is 120 DEG C;
In step (6), the temperature of pre-burning is 450 DEG C;
In step (8), the temperature of calcining is 800 DEG C;
In step (9), tempering 2h at 200 DEG C.
Embodiment 15
Composite doping modification positive electrode active materials LiMn
0.60mg
0.20zr
0.20vO
3.86i
0.14preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (1), take acetylacetone,2,4-pentanedione as part;
In step (2), 0.88:0.60:0.20:0.20:1.0:0.14 takes LiNO in molar ratio
3, Mn (OH)
2, Mg (CH
3cOO)
2, Zr (CH
3cOO)
4, NH
4vO
3and LiI;
In step (3), the ratio of Li ion, Mn ion, Mg ion, Zr ion, the mole sum of V ion and the mole of acetylacetone,2,4-pentanedione in the mixed solution of step (2) gained is 1:3;
In step (4), the temperature of heating water bath is 80 DEG C;
In step (5), vacuum drying temperature is 130 DEG C;
In step (6), the temperature of pre-burning is 500 DEG C;
In step (8), the temperature of calcining is 1000 DEG C;
In step (9), tempering 3h at 400 DEG C.
Embodiment 16
Composite doping modification positive electrode active materials LiMn
0.80cu
0.16mg
0.04vO
3.75i
0.25preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (1), take hydrogen peroxide as part;
In step (2), 0.77:0.80:0.16:0.04:1.0:0.25 takes LiOH, Mn (NO in molar ratio
3)
2, Cu (CH
3cOO)
2, Mg (CH
3cOO)
2, NH
4vO
3and LiI;
In step (3), the ratio of Li ion, Mn ion, Cu ion, Mg ion, the mole sum of V ion and the mole of hydrogen peroxide in the mixed solution of step (2) gained is 1:3;
In step (4), the temperature of heating water bath is 100 DEG C;
In step (5), vacuum drying temperature is 150 DEG C;
In step (6), the temperature of pre-burning is 600 DEG C;
In step (8), the temperature of calcining is 1200 DEG C;
In step (9), tempering 3h at 400 DEG C.
Comparative example 1
Positive electrode active materials LiCoVO
4preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (2), 1.02:1.0:1.0 takes LiNO in molar ratio
3, Co (NO
3)
2and NH
4vO
3;
In step (3), the ratio of Li ion, Co ion, the mole sum of V ion and the mole of ethylene glycol in the mixed solution of step (2) gained is 1:1;
Gained positive electrode active materials LiCoVO
4for the pure inverse spinel material not through any doping treatment.
Comparative example 2
Single doping vario-property positive electrode active materials LiCo
0.97al
0.03vO
4preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (2), 1.02:0.97:0.03:1.0 takes LiNO in molar ratio
3, Co (NO
3)
2, Al (NO
3)
3and NH
4vO
3;
In step (3), the ratio of Li ion, Co ion, Al ion, the mole sum of V ion and the mole of ethylene glycol in the mixed solution of step (2) gained is 1:1;
Gained list doping vario-property positive electrode active materials LiCo
0.97al
0.03vO
4for the inverse spinel material of single foreign cation modification.
Comparative example 3
Single doping vario-property positive electrode active materials LiCoVO
3.85f
0.15preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (2), 0.87:1.0:1.0:0.15 takes LiNO in molar ratio
3, Co (NO
3)
2, NH
4vO
3and LiF;
In step (3), the ratio of Li ion, Co ion, the mole sum of V ion and the mole of ethylene glycol in the mixed solution of step (2) gained is 1:1;
Gained list doping vario-property positive electrode active materials LiCoVO
3.85f
0.15for the inverse spinel material of single Doped anions modification.
Comparative example 4
Composite doping modification positive electrode active materials LiCo
0.97al
0.03vO
3.85f
0.15preparation, its by adopt the method identical with embodiment 1 prepare, difference is:
In step (1), part is ethylene glycol;
In step (2), 0.87:0.97:0.03:1.0:0.15 takes LiNO in molar ratio
3, Co (NO
3)
2, Al (NO
3)
3, NH
4vO
3, and LiF;
In step (3), the ratio of Li ion, Co ion, Al ion, the mole sum of V ion and the mole of ethylene glycol in the mixed solution of step (2) gained is 1:0.5;
In step (7) a metallic, the operation (namely the presoma of step (6) gained naturally cools to room temperature, afterwards at grinding in ball grinder 0.5 ~ 2h, becomes powder) of making base substrate is not carried out;
In step (8), the powder of step (7) gained is calcined 18h at 600 DEG C, naturally cools to room temperature afterwards, and then grind 0.5 ~ 2h on ball mill, become powder;
Step (9) does not perform (namely not carrying out tempering operation).
Provide the positive electrode active materials based on embodiment 1-16 and comparative example 1-4 below and the test carried out.
(1) each positive electrode active materials of embodiment 1-16 and comparative example 1-4 is carried out XRD detection, to obtain diffraction spectrogram, radiation source is Cu K α.
(2) each positive electrode active materials of embodiment 1-16 and comparative example 1-4 is carried out SEM detection, to obtain SEM image.
(3) prepare 2032 type button cells and carry out charge-discharge test
1) 2032 type button cells are prepared
The positive electrode active materials of embodiment 1-16 and comparative example 1-4 is mixed with the mass ratio of 80:12:8 with conductive agent acetylene black, binding agent Kynoar, with absolute ethyl alcohol as dispersant, uses ultrasonic oscillation to make it mix, obtain the slurry of thickness; Slurry is coated in current collector aluminum foil, makes circular pole piece with hydraulic press at 20MPa pressure, and at 120 DEG C vacuumize 12h; Adopt the circular pole piece of above-mentioned preparation to be positive pole, metal lithium sheet is negative pole, and Celgard2300 is barrier film, the LiPF of EC+DMC (volume ratio 1:1)+lmol/L
6for electrolyte, in argon gas atmosphere glove box, be assembled into 2032 type button cells.
2) charge-discharge test of 2032 type button cells
Test the working voltage platform of discharging first of 2032 type button cells, the first discharge specific capacity under 0.1C, the coulombic efficiency first under 0.1C, (0 ~ 20 circulation adopts 0.1C multiplying power for capability retention under 0.2C after 80 circulations, 21 ~ 60 circulations adopt 0.2C multiplying power, 61 ~ 70 circulations adopt 0.5C multiplying power, 71 ~ 80 circulations adopt 1.0C multiplying power), wherein, charging/discharging voltage scope is 2.5V ~ 5.0V.
Concrete discharge and recharge flow process is: under 0.1C multiplying power, constant current charge is to upper voltage limit 5.0V, then with 5.0V constant voltage charge to cut-off current 0.02C, then with 0.1C multiplying power constant-current discharge to lower voltage limit 2.5V.Discharge working voltage platform=discharge energy first/discharge capacity × 100% first first;
Quality × 100% of the discharge capacity/positive electrode active materials of first discharge specific capacity=first;
Coulombic efficiency first=discharge capacity first/initial charge capacity × 100%;
Discharge capacity/discharge capacity × 100% first after capability retention=80 time circulation after 80 circulations.
Table 1 provides parameter and the performance test results of embodiment 1-16 and comparative example 1-4.
Finally the performance test results of embodiment 1-16 and comparative example 1-4 is analyzed.
(1) XRD diffraction spectrogram and SEM graphical analysis
Fig. 1 is the XRD collection of illustrative plates of the composite doping modification positive electrode active materials of embodiment 1 gained.From the data in Fig. 1 and table 1, the position of the diffraction maximum of the composite doping modification positive electrode active materials of embodiment 1-8 gained and relative intensity are all coincide with standard JCPDS card, and it contains the characteristic peak of the strongest diffraction maximum (311) and inverse spinel: weak peak (111) and time strong peak (220).In Fig. 1, the peak type of each diffraction maximum is relatively more sharp-pointed, and the peak intensity of the strongest diffraction maximum (311) can reach 4000, and each diffraction maximum does not divide, and illustrates that the crystal formation of the composite doping modification material of gained is more perfect.In Fig. 1, each diffraction maximum is evenly single, does not have other impurity peaks, illustrates that the composite doping modification positive electrode active materials of gained is the inverse spinel structure of single crystalline phase.Relative to the XRD diffracting spectrum of embodiment 1-8, the weak peak (111) of the composite doping modification positive electrode active materials of embodiment 9-16 gained and 2 θ at time strong peak (220) become larger, the relative intensity at peak also more by force, more sharp-pointed, illustrate that the composite doping modification positive electrode active materials of embodiment 9-16 gained has the inverse spinel structure of more perfect single crystalline phase.And 2 θ at the weak peak (111) of the positive electrode active materials of comparative example 1-4 gained or composite doping modification positive electrode active materials and time strong peak (220) move to less direction, the relative intensity at peak is also more weak, although illustrate that the positive electrode active materials of comparative example 1-4 gained or composite doping modification positive electrode active materials are also inverse spinel structures, crystal formation is also imperfect.
Fig. 2 is the SEM image (amplifying 7000 times) of the composite doping modification positive electrode active materials of embodiment 1 gained.As can be seen from Figure 2, the grain diameter of composite doping modification positive electrode active materials evenly, be closely aligned together between smooth surface, particle, and the reunion mode of particle is interconnected from simply piling up to become, can make the combination between particle more closely like this and form microstructure, thus be conducive to the embedding of lithium ion and deviate from, and then promote tap density and the chemical property of composite doping modification positive electrode active materials.
The charge-discharge test analysis of (2) 2032 type button cells
Fig. 3 is the first charge-discharge curve chart of 2032 type button cells under 0.1C of embodiment 1 gained, Fig. 4 is that 2032 type button cells of the embodiment 1 gained first charge-discharge specific capacity under 0.1C is to the differential curve figure of charging/discharging voltage, Fig. 5 is 2032 type button cells of embodiment 1 gained and the first discharge curve of 2032 type button cells under 0.1C of comparative example 1 gained, Fig. 6 is that 2032 type button cells of 2032 type button cells of embodiment 1 gained and comparative example 1 gained are stage by stage at different multiplying (0.1C, 0.2C, 0.5C, cyclic curve figure 1.0C).
As can be seen from the contrast of embodiment 1-16 and comparative example 1-3, composite doping modification positive electrode active materials LirQ of the present invention
1-xm
xvO
4-yn
ycrystal formation more perfect, therefore there is higher electric discharge working voltage platform first, higher first discharge specific capacity and higher coulombic efficiency first, capability retention simultaneously after 80 circulations is also higher, this is mainly because the radius of the cation M of doping is moderate, there is larger octahedra potential energy, energy part substituted metal atom Q, thus the lattice of composite doping modification positive electrode active materials can be made to diminish, structure tends towards stability, and then improves the chemical property of composite doping modification positive electrode active materials.And the anion N of doping partly can replace O atom, thus effectively can increase the electron acceptor of composite doping modification positive electrode active materials, make forming section oxygen defect in crystal, in structure cell, vacancy volume increases, and is conducive to the embedding of lithium ion and deviates from.
As can be seen from the contrast of embodiment 1 and comparative example 1-3, through the inverse spinel material (embodiment 1) of composite doping modification process relative to not through the pure inverse spinel material (comparative example 1) of any doping treatment and the inverse spinel material (comparative example 2 and comparative example 3) of single modification by ion-doping process, its structure and shape characteristic more perfect, chemical property is also more excellent, working voltage platform of discharging first can raise about 0.2V, first discharge specific capacity can raise about 5mAh/g, coulombic efficiency can raise about 16% first, capability retention after 80 circulations can raise about 11%.
As can be seen from the contrast of embodiment 1 and comparative example 4, the composite doping modification positive electrode active materials of the sol-gal process synthesis optimized is used to have better chemical property, this is because the former with the addition of base operation before calcination, the effective supply of the air capacity in the generative process of composite doping modification positive electrode active materials can be ensured, make the composite doping modification positive electrode active materials of gained finer and close, structure is more stable simultaneously; Tempering operation simultaneously after calcining can make the composite doping modification positive electrode active materials effective temperature-reducing finalized the design almost, and makes crystal formation more stable and perfect, therefore can have better chemical property.
In sum, the Stability Analysis of Structures of composite doping modification positive electrode active materials of the present invention and pattern is good, adopts the lithium ion battery of composite doping modification positive electrode active materials of the present invention to have superior chemical property.
Claims (10)
1. a composite doping modification positive electrode active materials, is characterized in that, the general formula of described composite doping modification positive electrode active materials is Li
rq
1-xm
xvO
4-yn
ywherein, M, N are doped chemical, Q is the one in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, and M is at least one in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, Zr, La, Ti, Ca, Ba, B, Si, and N is at least one in F, Cl, Br, I, olivine-type polyanion, acid group, 0.6<r≤1.05,0<x≤0.25,0 < y≤0.30, and Q with M is not identical;
Li
rq
1-xm
xvO
4-yn
yfor space group Fd-3m (O
h 7), Li atom is in the space of octahedral coordination, and V atom is in the space of tetrahedral coordination, Li atom, position shared by metallic atom Q and doped chemical M are (16d, 1/2,1/2,1/2), the position shared by V atom is (8a, 1/4,1/4,1/4), O atom and the position shared by doped chemical N are (32e, x, x, x);
The XRD diffracting spectrum of described composite doping modification positive electrode active materials comprises the characteristic peak of the strongest diffraction maximum (311) and inverse spinel: weak peak (111) and time strong peak (220).
2. composite doping modification positive electrode active materials according to claim 1, is characterized in that,
Described metallic element Q is the one in Co, Ni, Mn, Cr;
Described doped chemical M is at least one in Cr, Al, Fe, Zr, La;
Described doped chemical N is at least one in F, Cl, Br.
3. composite doping modification positive electrode active materials according to claim 1, is characterized in that, 0.8<r≤1.02,0.01<x≤0.22,0.02<y≤0.25.
4. composite doping modification positive electrode active materials according to claim 1, is characterized in that, the charging/discharging voltage scope of described composite doping modification positive electrode active materials is 2.0V ~ 5.5V.
5. composite doping modification positive electrode active materials according to claim 4, is characterized in that, the charging/discharging voltage scope of described composite doping modification positive electrode active materials is 2.5V ~ 5.0V.
6. a preparation method for composite doping modification positive electrode active materials, for the preparation of the composite doping modification positive electrode active materials according to any one of claim 1-5, comprises step:
(1) part is dissolved in deionized water, forms ligand solution;
(2) Li salt, Q salt, M salt, V salt, N salt are dissolved in deionized water, form uniform mixed solution, wherein, Q is the one in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, M is at least one in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, Zr, La, Ti, Ca, Ba, B, Si, N is at least one in F, Cl, Br, I, olivine-type polyanion, acid group, and Q with M is not identical;
(3) mixed solution of step (2) gained is slowly joined in the ligand solution of step (1) gained, and under agitation form emulsion;
(4) by the emulsion of step (3) gained heating water bath at 60 DEG C ~ 100 DEG C, transpiring moisture, and constantly stir, obtain wet gel;
(5) by the vacuumize at 100 DEG C ~ 150 DEG C of the wet gel of step (4) gained, xerogel is obtained;
(6) by the pre-burning at 400 DEG C ~ 600 DEG C of the xerogel of step (5) gained, precursor is obtained;
(7) precursor of step (6) gained is naturally cooled to room temperature, make base substrate at grinding in ball grinder powdered afterwards;
(8) base substrate of step (7) gained is calcined at 600 DEG C ~ 1200 DEG C, naturally cool to after room temperature at grinding in ball grinder powdered;
(9) by the tempering at 100 DEG C ~ 400 DEG C of the powder of step (8) gained, obtain composite doping modification positive electrode active materials, the general formula of described composite doping modification positive electrode active materials is Li
rq
1-xm
xvO
4-yn
y, wherein, 0.6<r≤1.05,0<x≤0.25,0 < y≤0.30;
Li
rq
1-xm
xvO
4-yn
yfor space group Fd-3m (O
h 7), Li atom is in the space of octahedral coordination, and V atom is in the space of tetrahedral coordination, Li atom, position shared by metallic atom Q and doped chemical M are (16d, 1/2,1/2,1/2), the position shared by V atom is (8a, 1/4,1/4,1/4), O atom and the position shared by doped chemical N are (32e, x, x, x);
The XRD diffracting spectrum of described composite doping modification positive electrode active materials comprises the characteristic peak of the strongest diffraction maximum (311) and inverse spinel: weak peak (111) and time strong peak (220).
7. the preparation method of composite doping modification positive electrode according to claim 6, it is characterized in that, in step (1), described part is the one in oxalic acid, citric acid, tartaric acid, ethylenediamine tetra-acetic acid, ethylene glycol, acetylacetone,2,4-pentanedione, hydrogen peroxide, is preferably oxalic acid.
8. the preparation method of composite doping modification positive electrode active materials according to claim 6, it is characterized in that, in step (2), described Li salt, Q salt, M salt, V salt, Li ion in the mixed solution that N salt is formed, Q ion, M ion, V ion, the mol ratio of N ion is 1.02r:(1-x): x:1:y, wherein 0.6<r≤1.05, 0<x≤0.25, 0<y≤0.30, preferred 0.8<r≤1.02, 0.01<x≤0.22, 0.02<y≤0.25.
9. the preparation method of composite doping modification positive electrode active materials according to claim 6, it is characterized in that, Li ion in the mixed solution that described Li salt, Q salt, M salt, V salt, N salt are formed, Q ion, M ion, the mole sum of V ion are 1:(1 ~ 3 with the ratio of the mole of part), be preferably 1:2.
10. a lithium ion battery, comprising:
Anode pole piece, comprises composite doping modification positive electrode active materials;
Cathode pole piece;
Barrier film, is interval between anode pole piece and cathode pole piece; And
Electrolyte;
It is characterized in that, the composite doping modification positive electrode active materials of described composite doping modification positive electrode active materials according to any one of claim 1-5.
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| CN106252718A (en) * | 2016-10-19 | 2016-12-21 | 江苏海四达电源股份有限公司 | High power capacity electric tool column lithium ion battery and preparation method thereof |
| CN109616658A (en) * | 2018-12-17 | 2019-04-12 | 中科廊坊过程工程研究院 | A kind of selenium, the nickelic positive electrode of sulfate radical codope and its preparation method and application |
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| CN109860582A (en) * | 2018-12-28 | 2019-06-07 | 蜂巢能源科技有限公司 | Positive electrode of lithium ion battery and preparation method thereof |
| CN111653782A (en) * | 2020-06-12 | 2020-09-11 | 昆山宝创新能源科技有限公司 | Positive electrode material and preparation method and application thereof |
| CN112005409A (en) * | 2018-08-31 | 2020-11-27 | 松下知识产权经营株式会社 | Positive electrode active material and battery provided with same |
| CN113517433A (en) * | 2021-04-13 | 2021-10-19 | 天津理工大学 | Positive electrode material of anion-cation doped P2 type sodium ion battery |
| CN113830830A (en) * | 2021-09-16 | 2021-12-24 | 陕西理工大学 | Flake (NH) with iron and boron codope4)2V4O9Method for producing a material |
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| CN106252718A (en) * | 2016-10-19 | 2016-12-21 | 江苏海四达电源股份有限公司 | High power capacity electric tool column lithium ion battery and preparation method thereof |
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| CN109616658A (en) * | 2018-12-17 | 2019-04-12 | 中科廊坊过程工程研究院 | A kind of selenium, the nickelic positive electrode of sulfate radical codope and its preparation method and application |
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| CN109860582A (en) * | 2018-12-28 | 2019-06-07 | 蜂巢能源科技有限公司 | Positive electrode of lithium ion battery and preparation method thereof |
| CN109860582B (en) * | 2018-12-28 | 2022-04-19 | 蜂巢能源科技股份有限公司 | Positive electrode material of lithium ion battery and preparation method thereof |
| CN109738309A (en) * | 2019-01-31 | 2019-05-10 | 河北超威电源有限公司 | Lead charcoal power battery electrode board detecting method based on numerical analysis |
| CN109738309B (en) * | 2019-01-31 | 2021-07-20 | 河北超威电源有限公司 | Lead-carbon power battery pole plate detection method based on numerical analysis |
| CN111653782A (en) * | 2020-06-12 | 2020-09-11 | 昆山宝创新能源科技有限公司 | Positive electrode material and preparation method and application thereof |
| CN113517433A (en) * | 2021-04-13 | 2021-10-19 | 天津理工大学 | Positive electrode material of anion-cation doped P2 type sodium ion battery |
| CN113830830A (en) * | 2021-09-16 | 2021-12-24 | 陕西理工大学 | Flake (NH) with iron and boron codope4)2V4O9Method for producing a material |
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