CN105024067B - Lithium ion battery, composite doped modified positive active material thereof and preparation method - Google Patents
Lithium ion battery, composite doped modified positive active material thereof and preparation method Download PDFInfo
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Abstract
The invention provides a lithium ion battery, a composite doped modified positive active material thereof and a preparation method thereof. The general formula of the composite doping modified anode active material is LirQ1‑xMxVO4‑yNyWherein M, N is doped element, 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 polyanion and acid radical, 0.6<r≤1.05，0<x is less than or equal to 0.25, y is more than 0 and less than or equal to 0.30, and Q and M are different; the XRD diffraction pattern comprises the strongest diffraction peak (311) and the characteristic peak of inverse spinel: weak peak (111) and second-strong peak (220). The lithium ion battery comprises the composite doped modified positive active material. The composite doped modified positive active material has the advantages of stable structure and good appearance, and the first discharge working voltage platform, the first discharge specific capacity, the first coulombic efficiency and the capacity retention rate after multiple cycles of the lithium ion battery are high.
Description
Technical field
The present invention relates to field of batteries, more particularly to a kind of lithium ion battery and its composite doping modification positive electrode active materials
And preparation method.
Background technology
Lithium ion battery has the advantages that operating voltage is high, specific energy is big, had a safety feature, and is widely used in mobile logical
The portable electronic product such as news, notebook computer, as it is in pure electric vehicle, hybrid electric vehicle and large-scale energy storage field
Using the performance of, people to lithium ion battery, especially energy density and multiplying power density proposes higher requirement.Lithium-ion electric
The energy density in pond is relevant with the operating voltage of lithium ion battery and specific capacity, therefore seeks the lithium ion of high voltage and Large Copacity
The positive electrode active materials of battery have very important significance.
The positive electrode active materials of the lithium ion battery used at present, such as LiCoO2、LiMn2O4、LiFePO4、
LiNixCoyMn1-x-yO2Operating voltage be below 4V, the energy density and multiplying power density of lithium ion battery are above received in application
Limitation.Lithium-barium oxide is because of its high power capacity, low cost（The price of vanadium is low compared with cobalt, manganese）, turn into most the advantages of pollution-free, reserves are more
One of positive electrode active materials of lithium ion battery with development prospect.Because vanadium has multivalence, therefore VO can be formed2、V2O5、
V6O13、V4O9And V3O7Etc. a variety of barium oxides, these barium oxides can form stratiform lithium intercalation compound, and can form point
Spar type lithium intercalation compound and inverse spinel structure lithium intercalation compound, specific capacity reach as high as 334mAh/g.
In recent years, inverse spinel structure lithium-barium oxide causes people and greatly paid close attention to, in this compound, lithium atom
Space in octahedral coordination, vanadium atom is in the space of tetrahedral coordination.Compared with other types of lithium-barium oxide, instead
The cation degree of mixing of spinel-type lithium-barium oxide can reach 100%, and discharge voltage is much higher（LiNiVO4Up to 4.8V,
LiCoVO4Up to 4.2V）, the specific capacity of inverse spinel structure lithium-barium oxide can reach 148mAh/g in theory, but actual ratio
Capacity Ratio is relatively low, and its specific capacity is very fast with the increase attenuation ratio of cycle-index, so awaiting further exploring its knot
Structure, finds more preferably preparation method and effective modified method and improves its chemical property.The content of the invention
In view of problem present in background technology, it is an object of the invention to provide a kind of lithium ion battery and its compound mix
Miscellaneous modified positive electrode active materials and preparation method, the Stability Analysis of Structures of the composite doping modification positive electrode active materials, pattern are good,
The working voltage platform of electric discharge first of the lithium ion battery, first first discharge specific capacity, coulombic efficiency and repeatedly circulation
Capability retention afterwards is higher.
In order to realize foregoing invention purpose, in the first aspect of the present invention, the invention provides a kind of composite doping modification
Positive electrode active materials, its formula is LirQ1-xMxVO4-yNy, wherein, M, N be doped chemical, Q be Co, Ni, Mn, Cr, Al, Mg,
One kind in Fe, Cu, M is at least one of Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, Zr, La, Ti, Ca, Ba, B, Si, and N is
At least one of F, Cl, Br, I, olivine-type polyanion, acid group, 0.6<R≤1.05,0<X≤0.25,0 ＜ y≤0.30,
And Q and M are differed；LirQ1-xMxVO4-yNyFor space group Fd-3m (Oh 7), Li atoms are in the space of octahedral coordination, V atoms
Space in tetrahedral coordination, the position shared by Li atoms, metallic atom Q and doped chemical M is (16d, 1/2,1/2,1/
2), the position shared by V atoms is (8a, 1/4,1/4,1/4), O atom and position shared by doped chemical N for (32e, x, x,
x)；The XRD diffracting spectrums of the composite doping modification positive electrode active materials include most strong diffraction maximum（311）And inverse spinel
Characteristic peak：Weak peak（111）With secondary strong peak（220）.
In the second aspect of the present invention, the invention provides a kind of preparation side of composite doping modification positive electrode active materials
Method, for preparing composite doping modification positive electrode active materials according to a first aspect of the present invention, including step：（1）Part is molten
In deionized water, ligand solution is formed；（2）Li salt, Q salt, M salt, V salt, N salt are dissolved in deionized water, form uniform
Mixed solution, wherein, Q be Co, Ni, Mn, Cr, Al, Mg, Fe, Cu in one kind, M be Co, Ni, Mn, Cr, Al, Mg, Fe, Cu,
At least one of Zr, La, Ti, Ca, Ba, B, Si, N are at least one in F, Cl, Br, I, olivine-type polyanion, acid group
Plant, and Q and M are differed；（3）By step（2）The mixed solution of gained is slowly added into step（1）In the ligand solution of gained,
And emulsion is formed under agitation；（4）By step（3）The emulsion of gained heating water bath at 60 DEG C~100 DEG C, evaporates water
Point, and be stirred continuously, obtain wet gel；（5）By step（4）The wet gel of gained is dried in vacuo at 100 DEG C~150 DEG C, is obtained
To xerogel；（6）By step（5）The pre-burning at 400 DEG C~600 DEG C of the xerogel of gained, obtains precursor；（7）By step（6）
The precursor of gained naturally cools to room temperature, grind into powder and base substrate is made in ball mill afterwards；（8）By step（7）Institute
Base substrate calcined at 600 DEG C~1200 DEG C, naturally cool to after room temperature the grind into powder in ball mill；（9）By step
（8）The powder of gained is tempered at 100 DEG C~400 DEG C, obtains composite doping modification positive electrode active materials, described composite mixed to change
Property positive electrode active materials formula be LirQ1-xMxVO4-yNy, wherein, 0.6<R≤1.05,0<X≤0.25,0 ＜ y≤0.30；
LirQ1-xMxVO4-yNyFor space group Fd-3m (Oh 7), Li atoms are in the space of octahedral coordination, and V atoms are in tetrahedral coordination
Space, position shared by Li atoms, metallic atom Q and doped chemical M is (16d, 1/2,1/2,1/2), shared by V atoms
Position is (8a, 1/4,1/4,1/4), and O atom and the position shared by doped chemical N are (32e, x, x, x)；It is described composite mixed
The XRD diffracting spectrums of modified positive electrode active materials include most strong diffraction maximum（311）And the characteristic peak of inverse spinel：Weak peak
（111）With secondary strong peak（220）.
In the third aspect of the present invention, the invention provides a kind of lithium ion battery, it includes：Anode pole piece, including it is multiple
Close doping vario-property positive electrode active materials；Cathode pole piece；Barrier film, is interval between anode pole piece and cathode pole piece；And electrolysis
Liquid.The composite doping modification positive electrode active materials are the composite doping modification positive-active material according to first aspect present invention
Material.
Beneficial effects of the present invention are as follows：
（1）The single-phase free from admixture of composite doping modification positive electrode active materials, crystal property obtained by the present invention are good, grain diameter
Uniformly, surface is smooth.
（2）The present invention is by LirQVO4In positive electrode active materials mix Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, Zr, La,
The cations such as Ti, Ca, Ba, B, Si are partly to replace LirQVO4In metallic atom Q, the poly- the moon of incorporation F, Cl, Br, I, olivine-type
The anion such as ion, acid group are partly to replace LirQVO4In O atom, the mode of this Anion-cation multiple dope can take into account sun
The rock-steady structure of ion, while playing the cooperative effect of anion, makes the electric discharge operating voltage first of the lithium ion battery of gained
Capability retention after platform, first first discharge specific capacity, coulombic efficiency and multiple circulation is higher.
（3）The preparation method of the composite doping modification positive electrode active materials of the present invention is easy to operate, and technique is simple, and cost is low
It is honest and clean, it is easy to implement and carry out industrialized production.
Brief description of the drawings
Fig. 1 is the X-ray diffraction of the composite doping modification positive electrode active materials of the gained of the embodiment of the present invention 1（XRD）Collection of illustrative plates.
Fig. 2 is the SEM of the composite doping modification positive electrode active materials of the gained of the embodiment of the present invention 1（SEM）
Image.
Fig. 3 is the first charge-discharge curve map of 2032 type button cells of the gained of the embodiment of the present invention 1.
Fig. 4 is the first charge-discharge specific capacity of 2032 type button cells of the gained of the embodiment of the present invention 1 to charging/discharging voltage
Differential curve figure.
Fig. 5 is the embodiment of the present invention 1 and the discharge curve comparison diagram first of 2032 type button cells of the gained of comparative example 1.
Fig. 6 is 2032 type button cells obtained by the embodiment of the present invention 1 and comparative example 1 following under different multiplying stage by stage
Ring curve comparison figure.
Embodiment
The following detailed description of the lithium ion battery according to the present invention and its composite doping modification positive electrode active materials and preparation
Method and embodiment, comparative example and test result.
Illustrate composite doping modification positive electrode active materials according to a first aspect of the present invention first.
Composite doping modification positive electrode active materials according to a first aspect of the present invention, its formula is LirQ1-xMxVO4-yNy, its
In, M, N be doped chemical, Q be Co, Ni, Mn, Cr, Al, Mg, Fe, Cu in one kind, M be Co, Ni, Mn, Cr, Al, Mg, Fe,
At least one of Cu, Zr, La, Ti, Ca, Ba, B, Si, N be F, Cl, Br, I, olivine-type polyanion, acid group at least
One kind, 0.6<R≤1.05,0<X≤0.25,0 ＜ y≤0.30, and Q and M differ；LirQ1-xMxVO4-yNyFor space group Fd-3m
(Oh 7), Li atoms be in octahedral coordination space, V atoms be in tetrahedral coordination space, Li atoms, metallic atom Q with
And the position shared by doped chemical M is (16d, 1/2,1/2,1/2), the position shared by V atoms 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 of the composite doping modification positive electrode active materials spreads out
Penetrate collection of illustrative plates and include most strong diffraction maximum（311）And the characteristic peak of inverse spinel：Weak peak（111）With secondary strong peak（220）.
In the composite doping modification positive electrode active materials Li of the present inventionrQ1-xMxVO4-yNyIn, the doped chemical M portions of cation
Divide substituted metal atom Q, the lattice of composite doping modification positive electrode active materials can be made to diminish, structure tends towards stability, Jin Ergai
The chemical property of kind composite doping modification positive electrode active materials, improves the cycle life of lithium ion battery；And anion is mixed
Miscellaneous element N section replaces O atom, can effectively increase the electron acceptor of composite doping modification positive electrode active materials, make crystal
Vacancy volume increase in middle formation part oxygen defect, structure cell, so as to be conducive to the insertion and abjection of lithium ion.
The mode of Anion-cation multiple dope can comprehensively utilize the advantage of zwitterion, while enabling their shortcoming to the greatest extent can
It can cancel out each other, and make it produce cooperative effect to improve the combination property of lithium ion battery.Anion-cation multiple dope is not only
The crystallinity and tap density of positive electrode active materials can be improved, moreover it is possible to improve the electrochemistry of positive electrode active materials under high pressure
Can, and then improve the cycle performance of lithium ion battery, and the initial specific capacities of positive electrode active materials increase, and then lithium ion
The capability retention of battery is also higher.
In composite doping modification positive electrode active materials described according to a first aspect of the present invention, the metallic element Q is excellent
Choosing can be one kind in Co, Ni, Mn, Cr；The doped chemical M preferably can be at least one of Cr, Al, Fe, Zr, La；Institute
It preferably can be at least one of F, Cl, Br to state doped chemical N.Preferably in the doped chemical M of transition metal electron configuration
Containing single electron, the valency layer d tracks with underfill, based on eighteen-electron rule, its property have significant difference with other members,
Can with the presence of plurality of stable valence state ion.And preferably have 7 electronics on the doped chemical N of halogen outermost electron, have
The tendency of 1 halogen ion for electronically forming stable octet structure is obtained, thus with stronger electronegativity, chemical property ratio
It is more active.Therefore present invention preferably employs the two（That is doped chemical M uses transition metal, and doped chemical N is halogen）To anti-point
Spar type positive electrode active materials carry out composite doping modification, are ensureing inverse spinel structure positive electrode active materials lattice and Stability Analysis of Structures
On the premise of, 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, it is preferable that 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 composite doping modification
The charging/discharging voltage scope of positive electrode active materials can be 2.0V~5.5V, preferably can be 2.5V~5.0V, to ensure in discharge and recharge
During lithium ion can be completely embedded into and deviate from composite doping modification positive electrode active materials, and ensure redox reaction
Fully carry out, and then lithium ion battery is shown excellent chemical property.
Secondly the preparation method of composite doping modification positive electrode active materials according to a second aspect of the present invention is illustrated.
The preparation method of composite doping modification positive electrode active materials according to a second aspect of the present invention, including step：（1）Will
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, formed
Uniform mixed solution, wherein, Q is one kind in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, M be Co, Ni, Mn, Cr, Al, Mg,
At least one of Fe, Cu, Zr, La, Ti, Ca, Ba, B, Si, N is in F, Cl, Br, I, olivine-type polyanion, acid group
At least one, and Q and M differ；（3）By step（2）The mixed solution of gained is slowly added into step（1）The part of gained is molten
In liquid, and emulsion is formed under agitation；（4）By step（3）The emulsion of gained heating water bath at 60 DEG C~100 DEG C, steams
Shampoo point, and be stirred continuously, obtain wet gel；（5）By step（4）The wet gel of gained vacuum at 100 DEG C~150 DEG C is done
It is dry, obtain xerogel；（6）By step（5）The pre-burning at 400 DEG C~600 DEG C of the xerogel of gained, obtains precursor；（7）Will step
Suddenly（6）The precursor of gained naturally cools to room temperature, grind into powder and base substrate is made in ball mill afterwards；（8）By step
（7）The base substrate of gained is calcined at 600 DEG C~1200 DEG C, naturally cools to after room temperature the grind into powder in ball mill；（9）Will
Step（8）The powder of gained is tempered at 100 DEG C~400 DEG C, obtains composite doping modification positive electrode active materials, and described be combined is mixed
The formula of miscellaneous modified positive electrode active materials is LirQ1-xMxVO4-yNy, wherein, 0.6<R≤1.05,0<X≤0.25,0 ＜ y≤
0.30；LirQ1-xMxVO4-yNyFor space group Fd-3m (Oh 7), Li atoms are in the space of octahedral coordination, and V atoms are in four sides
The space of body coordination, the position shared by Li atoms, metallic atom Q and doped chemical M is (16d, 1/2,1/2,1/2), V atoms
Shared position is (8a, 1/4,1/4,1/4), and O atom and the position shared by doped chemical N are (32e, x, x, x)；It is described multiple
The XRD diffracting spectrums for closing doping vario-property positive electrode active materials include most strong diffraction maximum（311）And the characteristic peak of inverse spinel：It is weak
Peak（111）With secondary 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）In, the part can be in oxalic acid, citric acid, tartaric acid, ethylenediamine tetra-acetic acid, ethylene glycol, acetylacetone,2,4-pentanedione, hydrogen peroxide
One kind, 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）In, the Li salt can be one kind 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）In, the Q salt can be one in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu acetate, nitrate, halogen, hydroxide
Kind, preferably can be Co, Ni, Mn, Cr, Al halogen.
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）In, the V salt can be one kind in ammonium metavanadate, vanadic anhydride, 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）In, the M salt can for Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, Zr, La, Ti, Ca, Ba, B, Si acetate, nitrate,
At least one of halogen, hydroxide, preferably can be Co, Ni, Mn, Cr, Al, Fe, Zr, La in two kinds of metals halogen.
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）In, the N salt can at least one of for F, Cl, Br, I, olivine-type polyanion, the lithium salts of acid group, sodium salt, sylvite,
It is preferred that can be F, Cl, Br lithium salts.In the system of composite doping modification positive electrode active materials described according to a second aspect of the present invention
In Preparation Method, the Li salt, Q salt, M salt, V salt, the Li ions in the mixed solution of N salt formation, Q ions, M ions, V ions, N
The mol ratio of 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 sun from
When sub- M doping is less than 0.01, it can not effectively replace original Q atoms, so that stable lattice can not be formed；Work as sun
When ion M doping is higher than 0.25, then excessive cation M can be made to enter intracell, the position of Li atoms is occupied, cause
The reduction of reversible deintercalation Li, part lattice caves in, and specific discharge capacity declines, and the chemical property of lithium ion battery is deteriorated；When
When the doping of anion N is less than 0.01, it can not effectively replace original O atom, so that stable lattice can not be formed；When
When the doping of anion N is higher than 0.3, then it can replace original O atom because of excessive anion N, cause crystal oxygen defect mistake
Vacancy volumetric expansion failure in degree, structure cell, is unfavorable for the insertion and abjection of lithium ion.Therefore preferably 0.8<R≤1.02,
0.01<X≤0.22,0.02<Y≤0.25, the composite doping modification positive electrode active materials prepared using preferred scope are had 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）In, the Li salt, Q salt, M salt, V salt, the Li ions in the mixed solution of N salt formation, Q ions, M ions, V ions rub
It can be 1 that you, which measure the ratio between sum and the mole of part,:(1~3), preferably can be 1:2, it can so ensure composite doping modification positive pole
Active material gel and precursor in building-up process are effectively formed, while will not mix that some later stages are difficult to remove is miscellaneous
Matter, and then ensure the microscopic appearance and crystalline structure of composite doping modification positive electrode active materials, so that lithium ion battery has
There is 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）In, 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）In, 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）In, 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）In, 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）In, 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）In, 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）In, the time of tempering can be no longer than 4h.
When each step（Step（4）To step（9））Treatment temperature and processing time, especially heating water bath（Step
（4））With xerogel pre-burning（Step（6））Temperature and time not at that time, the specific capacity of composite doping modification positive electrode active materials
Improvement with cycle performance is not obvious, and this is probably, because doping level is not very perfect, to cause doped chemical and positive pole
The combination of active material is obtained and built on the sand, in the case where crossing high temperature and calcining for a long time excessively, doped chemical can largely enter body phase
In structure, rock-steady structure can not be played a part of, can not play a part of improving crystal structure and chemical property, and not
Beneficial to being produced.
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）In, 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）In, 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）In, 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）In, the instrument of base substrate calcining can be ceramic crucible.
The selection of suitable heat time, calcination time and instrument, it is ensured that the abundant progress of synthetic reaction and will not
Make overreact, just on the premise of the purity of synthetic material is ensured, can so be further ensured that synthetic material microscopic appearance,
Crystal structure and chemical property.
Illustrate lithium ion battery according to a third aspect of the present invention again.
Lithium ion battery according to a third aspect of the present invention, including：Anode pole piece, including composite doping modification positive-active
Material；Cathode pole piece；Barrier film, is interval between anode pole piece and cathode pole piece；And electrolyte.The composite doping modification
Positive electrode active materials are the composite doping modification positive electrode active materials according to first aspect present invention.
In lithium ion battery described according to a third aspect of the present invention, the positive conductive agent can be acetylene black；It is described
Positive electrode binder can be polytetrafluoroethylene (PTFE)；The positive pole dispersant can be absolute ethyl alcohol；The plus plate current-collecting body can be aluminium foil.
In lithium ion battery described according to a third aspect of the present invention, the cathode pole piece can be metal lithium sheet.
In lithium ion battery described according to a third aspect of the present invention, the barrier film can be Celgard2300.
In lithium ion battery described according to a third aspect of the present invention, the voltage of the lithium ion battery charge-discharge test
Scope can be 2.0V~5.5V, preferably can be 2.5V~5.0V.
Finally illustrate the lithium ion battery and its composite doping modification positive electrode active materials and preparation method according to the present invention
Embodiment and comparative example and test process and test result.
Embodiment 1
Composite doping modification positive electrode active materials LiCo0.97Al0.03VO3.85F0.15Preparation, it passes through following steps system
It is standby：
（1）Part ethylene glycol is dissolved in deionized water and obtains saturation ethylene glycol ligand solution；
（2）In molar ratio 0.87:0.97:0.03:1:0.15 weighs LiNO3、Co(NO3)2、Al(NO3)3、NH4VO3And
LiF is simultaneously dissolved in deionized water, is sufficiently stirred for obtaining mixed solution；
（3）By step（2）The mixed solution of gained is slowly added into step（1）The saturation ethylene glycol ligand solution of gained
In, and emulsion is obtained under 1200r/min high-speed stirred, wherein, step（2）Li ions in the mixed solution of gained,
Co ions, Al ions, the ratio of the mole of the mole sum of V ions and ethylene glycol are 1:1；
（4）By step（3）The emulsion of gained heating water bath 12h at 60 DEG C, to evaporate moisture, and is stirred continuously, obtains
To wet gel, wherein, mixing speed is 300r/min；
（5）By step（4）The wet gel of gained dries 6h in 100 DEG C of vacuum drying chambers, obtains xerogel；
（6）By step（5）The xerogel of gained pre-burning 3h at 400 DEG C, obtains presoma；
（7）By step（6）The presoma of gained naturally cools to room temperature, grinds 0.5~2h in ball mill afterwards, makes it
As powder and base substrate is made；
（8）By step（7）The base substrate of gained calcines 18h at 600 DEG C, and room temperature is naturally cooled to afterwards, is then existed again
1.5h is ground on ball mill, powder is become；
（9）By step（8）The powder of gained is tempered 1h at 100 DEG C, that is, obtains composite doping modification positive electrode active materials
LiCo0.97Al0.03VO3.85F0.15。
Embodiment 2
Composite doping modification positive electrode active materials LiCo0.93Cr0.07VO3.90F0.10Preparation, its by using with embodiment
Prepared by 1 identical method, difference is：
In step（1）In, using oxalic acid as part；
In step（2）In, in molar ratio 0.92:0.93:0.07:1:0.10 weighs LiOH, Co (NO3)2、Cr(NO3)3、
NH4VO3And LiF；
In step（3）In, step（2）Li ions, Co ions, Cr ions, mole of V ions in the mixed solution of gained
The ratio for measuring sum and the mole of oxalic acid is 1:2；
In step（4）In, the temperature of heating water bath is 70 DEG C；
In step（5）In, vacuum drying temperature is 120 DEG C；
In step（6）In, the temperature of pre-burning is 450 DEG C；
In step（8）In, the temperature of calcining is 800 DEG C.
Embodiment 3
Composite doping modification positive electrode active materials LiCo0.85Fe0.15VO3.92Cl0.08Preparation, its by using with implementation
Prepared by the identical method of example 1, difference is：
In step（1）In, using acetylacetone,2,4-pentanedione as part；
In step（2）In, in molar ratio 0.94:0.85:0.15:1:0.08 weighs CH3COOLi、Co(CH3COO)2、Fe
(NO3)3、NH4VO3And LiCl；
In step（3）In, step（2）Li ions, Co ions, Fe ions, mole of V ions in the mixed solution of gained
The ratio for measuring sum and the mole of acetylacetone,2,4-pentanedione is 1:3；
In step（4）In, the temperature of heating water bath is 80 DEG C；
In step（5）In, vacuum drying temperature is 130 DEG C；
In step（6）In, the temperature of pre-burning is 500 DEG C；
In step（8）In, the temperature of calcining is 1000 DEG C；
In step（9）In, it is tempered 2h at 200 DEG C.
Embodiment 4
Composite doping modification positive electrode active materials LiCo0.80La0.20VO3.80Cl0.20Preparation, its by using with implementation
Prepared by the identical method of example 1, difference is：
In step（1）In, using hydrogen peroxide as part；
In step（2）In, in molar ratio 0.82:0.80:0.20:1.0:0.20 weighs LiNO3、Co(CH3COO)2、
LaCl3、NH4VO3And LiCl；
In step（3）In, step（2）Li ions, Co ions, La ions, mole of V ions in the mixed solution of gained
The ratio for measuring sum and the mole of hydrogen peroxide is 1:3；
In step（4）In, the temperature of heating water bath is 100 DEG C；
In step（5）In, vacuum drying temperature is 150 DEG C；
In step（6）In, the temperature of pre-burning is 600 DEG C；
In step（8）In, the temperature of calcining is 1200 DEG C；
In step（9）In, it is tempered 2h at 200 DEG C.
Embodiment 5
Composite doping modification positive electrode active materials LiCr0.85Mg0.15VO3.96Br0.04Preparation, its by using with implementation
Prepared by the identical method of example 1, difference is：
In step（2）In, in molar ratio 0.98:0.85:0.15:1.0:0.04 weighs LiNO3、Cr(CH3COO)3、
MgCl2、NH4VO3And LiBr；
In step（3）In, step（2）Li ions, Cr ions, Mg ions, mole of V ions in the mixed solution of gained
The ratio for measuring sum and the mole of ethylene glycol is 1:1；
In step（9）In, it is tempered 2h at 200 DEG C.
Embodiment 6
Composite doping modification positive electrode active materials LiCr0.95Co0.05VO3.94Br0.06Preparation, its by using with implementation
Prepared by the identical method of example 1, difference is：
In step（1）In, using oxalic acid as part；
In step（2）In, in molar ratio 0.96:0.95:0.05:1.0:0.06 weighs LiNO3、Cr(CH3COO)3、
CoCl2、NH4VO3And LiBr；
In step（3）In, step（2）Li ions, Cr ions, Co ions, mole of V ions in the mixed solution of gained
The ratio for measuring sum and the mole of oxalic acid is 1:2；
In step（4）In, the temperature of heating water bath is 70 DEG C；
In step（5）In, vacuum drying temperature is 120 DEG C；
In step（6）In, the temperature of pre-burning is 450 DEG C；
In step（8）In, the temperature of calcining is 800 DEG C；
In step（9）In, it is tempered 2h at 200 DEG C.
Embodiment 7
Composite doping modification positive electrode active materials LiCr0.94Zr0.06VO3.92I0.08Preparation, its by using with embodiment
Prepared by 1 identical method, difference is：
In step（1）In, using acetylacetone,2,4-pentanedione as part；
In step（2）In, in molar ratio 0.94:0.94:0.06:1.0:0.08 weighs LiNO3、CrCl3、Zr
(CH3COO)4、NH4VO3And LiI；
In step（3）In, step（2）Li ions, Cr ions, Zr ions, mole of V ions in the mixed solution of gained
The ratio for measuring sum and the mole of acetylacetone,2,4-pentanedione is 1:3；
In step（4）In, the temperature of heating water bath is 80 DEG C；
In step（5）In, vacuum drying temperature is 130 DEG C；
In step（6）In, the temperature of pre-burning is 500 DEG C；
In step（8）In, the temperature of calcining is 1000 DEG C；
In step（9）In, it is tempered 3h at 400 DEG C.
Embodiment 8
Composite doping modification positive electrode active materials LiCr0.82Cu0.18VO3.84I0.16Preparation, its by using with embodiment
Prepared by 1 identical method, difference is：
In step（1）In, using hydrogen peroxide as part；
In step（2）In, in molar ratio 0.86:0.82:0.18:1.0:0.16 weighs CH3COOLi、CrCl3、Cu
(NO3)2、NH4VO3And LiI；
In step（3）In, step（2）Li ions, Cr ions, Cu ions, mole of V ions in the mixed solution of gained
The ratio for measuring sum and the mole of hydrogen peroxide is 1:3；
In step（4）In, the temperature of heating water bath is 100 DEG C；
In step（5）In, vacuum drying temperature is 150 DEG C；
In step（6）In, the temperature of pre-burning is 600 DEG C；
In step（8）In, the temperature of calcining is 1200 DEG C；
In step（9）In, it is tempered 3h at 400 DEG C.
Embodiment 9
Composite doping modification positive electrode active materials LiNi0.86Al0.10Cu0.04VO3.90F0.10Preparation, its by using with reality
The preparation of the identical method of example 1 is applied, difference is：
In step（2）In, in molar ratio 0.92:0.86:0.10:0.04:0.5:0.10 weighs CH3COOLi、Ni(OH)2、
Al(NO3)3、Cu(NO3)2、V2O5And LiF；
In step（3）In, step（2）Li ions, Ni ions, Al ions, Cu ions, V in the mixed solution of gained from
The ratio of the mole sum of son and the mole of ethylene glycol is 1:1；
Embodiment 10
Composite doping modification positive electrode active materials LiNi0.96Cr0.02La0.02VO3.98F0.02Preparation, its by using with reality
The preparation of the identical method of example 1 is applied, difference is：
In step（1）In, using oxalic acid as part；
In step（2）In, in molar ratio 1.0:0.96:0.02:0.02:0.5:0.02 weighs LiCl, NiCl2、Cr
(NO3)2、La(NO3)3、V2O5And LiF；
In step（3）In, step（2）Li ions, Ni ions, Cr ions, La ions, V in the mixed solution of gained from
The ratio of the mole sum of son and the mole of oxalic acid is 1:2；
In step（4）In, the temperature of heating water bath is 70 DEG C；
In step（5）In, vacuum drying temperature is 120 DEG C；
In step（6）In, the temperature of pre-burning is 450 DEG C；
In step（8）In, the temperature of calcining is 800 DEG C.
Embodiment 11
Composite doping modification positive electrode active materials LiNi0.94Zr0.04Fe0.02VO3.96Cl0.04Preparation, its by using with
Prepared by the identical method of embodiment 1, difference is：
In step（1）In, using acetylacetone,2,4-pentanedione as part；
In step（2）In, in molar ratio 0.49:0.94:0.04:0.02:0.5:0.04 weighs Li2CO3、NiCl2、Zr
(NO3)4、Fe(NO3)3、V2O5And LiCl；
In step（3）In, step（2）Li ions, Ni ions, Zr ions, Fe ions, V in the mixed solution of gained from
The ratio of the mole sum of son and the mole of acetylacetone,2,4-pentanedione is 1:3；
In step（4）In, the temperature of heating water bath is 80 DEG C；
In step（5）In, vacuum drying temperature is 130 DEG C；
In step（6）In, the temperature of pre-burning is 500 DEG C；
In step（8）In, the temperature of calcining is 1000 DEG C；
In step（9）In, it is tempered 2h at 200 DEG C.
Embodiment 12
Composite doping modification positive electrode active materials LiNi0.90Fe0.06La0.04VO3.94Cl.006Preparation, its by using with
Prepared by the identical method of embodiment 1, difference is：
In step（1）In, using hydrogen peroxide as part；
In step（2）In, in molar ratio 0.48:0.90:0.06:0.04:0.5:0.06 weighs Li2CO3、Ni(OH)2、Fe
(NO3)3、La(NO3)3、V2O5And LiCl；
In step（3）In, step（2）Li ions, Ni ions, Fe ions, La ions, V in the mixed solution of gained from
The ratio of the mole sum of son and the mole of hydrogen peroxide is 1:3；
In step（4）In, the temperature of heating water bath is 100 DEG C；
In step（5）In, vacuum drying temperature is 150 DEG C；
In step（6）In, the temperature of pre-burning is 600 DEG C；
In step（8）In, the temperature of calcining is 1200 DEG C；
In step（9）In, it is tempered 2h at 200 DEG C.
Embodiment 13
Composite doping modification positive electrode active materials LiMn0.88Al0.07Co0.05VO3.90Br0.10Preparation, its by using with
Prepared by the identical method of embodiment 1, difference is：
In step（2）In, in molar ratio 0.92:0.88:0.07:0.05:1.0:0.10 weighs LiOH, MnCl2、Al
(NO3)3、Co(NO3)3、NH4VO3And LiBr；
In step（3）In, step（2）Li ions, Mn ions, Al ions, Co ions, V in the mixed solution of gained from
The ratio of the mole sum of son and the mole of ethylene glycol is 1:1；
In step（9）In, it is tempered 2h at 200 DEG C.
Embodiment 14
Composite doping modification positive electrode active materials LiMn0.86Cr0.08Cu0.06VO3.88Br0.12Preparation, its by using with
Prepared by the identical method of embodiment 1, difference is：
In step（1）In, using oxalic acid as part；
In step（2）In, in molar ratio 0.9:0.86:0.08:0.06:1.0:0.12 weighs LiOH, MnCl2、Cr
(NO3)3、Cu(NO3)2、NH4VO3And LiBr；
In step（3）In, step（2）Li ions, Mn ions, Cr ions, Cu ions, V in the mixed solution of gained from
The ratio of the mole sum of son and the mole of oxalic acid is 1:2；
In step（4）In, the temperature of heating water bath is 70 DEG C；
In step（5）In, vacuum drying temperature is 120 DEG C；
In step（6）In, the temperature of pre-burning is 450 DEG C；
In step（8）In, the temperature of calcining is 800 DEG C；
In step（9）In, it is tempered 2h at 200 DEG C.
Embodiment 15
Composite doping modification positive electrode active materials LiMn0.60Mg0.20Zr0.20VO3.86I0.14Preparation, its by using with reality
The preparation of the identical method of example 1 is applied, difference is：
In step（1）In, using acetylacetone,2,4-pentanedione as part；
In step（2）In, in molar ratio 0.88:0.60:0.20:0.20:1.0:0.14 weighs LiNO3、Mn(OH)2、Mg
(CH3COO)2、Zr(CH3COO)4、NH4VO3And LiI；
In step（3）In, step（2）Li ions, Mn ions, Mg ions, Zr ions, V in the mixed solution of gained from
The ratio of the mole sum of son and the mole of acetylacetone,2,4-pentanedione is 1:3；
In step（4）In, the temperature of heating water bath is 80 DEG C；
In step（5）In, vacuum drying temperature is 130 DEG C；
In step（6）In, the temperature of pre-burning is 500 DEG C；
In step（8）In, the temperature of calcining is 1000 DEG C；
In step（9）In, it is tempered 3h at 400 DEG C.
Embodiment 16
Composite doping modification positive electrode active materials LiMn0.80Cu0.16Mg0.04VO3.75I0.25Preparation, its by using with reality
The preparation of the identical method of example 1 is applied, difference is：
In step（1）In, using hydrogen peroxide as part；
In step（2）In, in molar ratio 0.77:0.80:0.16:0.04:1.0:0.25 weighs LiOH, Mn (NO3)2、Cu
(CH3COO)2、Mg(CH3COO)2、NH4VO3And LiI；
In step（3）In, step（2）Li ions, Mn ions, Cu ions, Mg ions, V in the mixed solution of gained from
The ratio of the mole sum of son and the mole of hydrogen peroxide is 1:3；
In step（4）In, the temperature of heating water bath is 100 DEG C；
In step（5）In, vacuum drying temperature is 150 DEG C；
In step（6）In, the temperature of pre-burning is 600 DEG C；
In step（8）In, the temperature of calcining is 1200 DEG C；
In step（9）In, it is tempered 3h at 400 DEG C.
Comparative example 1
Positive electrode active materials LiCoVO4Preparation, it is prepared by using method same as Example 1, difference
It is：
In step（2）In, in molar ratio 1.02:1.0:1.0 weigh LiNO3、Co(NO3)2And NH4VO3；
In step（3）In, step（2）Li ions, Co ions, the mole sum of V ions in the mixed solution of gained
Ratio with the mole of ethylene glycol is 1:1；
Gained positive electrode active materials LiCoVO4For no pure inverse spinel material Jing Guo any doping treatment.
Comparative example 2
Single doping vario-property positive electrode active materials LiCo0.97Al0.03VO4Preparation, it is by using same as Example 1
Prepared by method, difference is：
In step（2）In, in molar ratio 1.02:0.97:0.03:1.0 weigh LiNO3、Co(NO3)2、Al(NO3)3And
NH4VO3；
In step（3）In, step（2）Li ions, Co ions, Al ions, mole of V ions in the mixed solution of gained
The ratio for measuring sum and the mole of ethylene glycol is 1:1；
Gained list doping vario-property positive electrode active materials LiCo0.97Al0.03VO4For the anti-point of single foreign cation modification
Spinel.
Comparative example 3
Single doping vario-property positive electrode active materials LiCoVO3.85F0.15Preparation, it is by using side same as Example 1
Prepared by method, difference is：
In step（2）In, in molar ratio 0.87:1.0:1.0:0.15 weighs LiNO3、Co(NO3)2、NH4VO3And LiF；
In step（3）In, step（2）Li ions, Co ions, the mole sum of V ions in the mixed solution of gained
Ratio with the mole of ethylene glycol is 1:1；
Gained list doping vario-property positive electrode active materials LiCoVO3.85F0.15It is brilliant for the anti-point of single Doped anions modification
Stone material.
Comparative example 4
Composite doping modification positive electrode active materials LiCo0.97Al0.03VO3.85F0.15Preparation, its by using with embodiment
Prepared by 1 identical method, difference is：
In step（1）In, part is ethylene glycol；
In step（2）In, in molar ratio 0.87:0.97:0.03:1.0:0.15 weighs LiNO3、Co(NO3)2、Al(NO3)3、
NH4VO3And LiF；
In step（3）In, step（2）Li ions, Co ions, Al ions, mole of V ions in the mixed solution of gained
The ratio for measuring sum and the mole of ethylene glycol is 1:0.5；
In step（7）In, without the operation that base substrate is made（That is step（6）The presoma of gained naturally cools to room temperature,
0.5~2h is ground in ball mill afterwards, powder is become）；
In step（8）In, by step（7）The powder of gained calcines 18h at 600 DEG C, room temperature is naturally cooled to afterwards, so
Grind 0.5~2h on ball mill again afterwards, become powder；
Step（9）Do not perform（I.e. without tempering operation）.
The test that the positive electrode active materials based on embodiment 1-16 and comparative example 1-4 are given below and carry out.
（1）Embodiment 1-16 and comparative example 1-4 each positive electrode active materials are subjected to XRD detections, to obtain diffraction spectrogram,
Radiation source is Cu K α.
（2）Embodiment 1-16 and comparative example 1-4 each positive electrode active materials are subjected to SEM detections, to obtain SEM image.
（3）Prepare 2032 type button cells and carry out charge-discharge test
1）Prepare 2032 type button cells
By embodiment 1-16 and comparative example 1-4 positive electrode active materials and conductive agent acetylene black, binding agent Kynoar
With 80:12:8 mass ratio mixing, with absolute ethyl alcohol as dispersant, is well mixed it using ultrasonic oscillation, is glued
Thick slurry；Slurry is coated in current collector aluminum foil, circular pole piece is pressed under 20MPa pressure with hydraulic press, and 120
12h is dried in vacuo at DEG C；The circular pole piece of above-mentioned preparation is used for positive pole, metal lithium sheet is negative pole, Celgard2300 is isolation
Film, EC+DMC (volume ratios 1:1)+lmol/L LiPF6For electrolyte, 2032 type buttons are assembled into argon gas atmosphere glove box
Battery.
2）The charge-discharge test of 2032 type button cells
Test 2032 type button cells first electric discharge working voltage platform, the first discharge specific capacity under 0.1C,
Coulombic efficiency first under 0.1C, the capability retention under 0.2C after 80 circulations（0~20 circulation uses 0.1C multiplying powers,
21~60 circulations use 0.2C multiplying powers, and 61~70 circulations use 0.5C multiplying powers, and 71~80 circulations use 1.0C multiplying powers）,
Wherein, charging/discharging voltage scope is 2.5V~5.0V.
Specifically discharge and recharge flow is：Then constant-current charge is filled to upper voltage limit 5.0V with 5.0V constant pressures under 0.1C multiplying powers
Electricity is to cut-off current 0.02C, then with 0.1C multiplying powers constant-current discharge to lower voltage limit 2.5V.Discharge working voltage platform=head first
Discharge capacity × 100% of secondary discharge energy/first；
Quality × 100% of the discharge capacity/positive electrode active materials of first discharge specific capacity=first；
Discharge capacity/initial charge capacity × 100% of coulombic efficiency=first first；
Discharge capacity × 100% of discharge capacity/first after the circulation of capability retention=80 time after 80 circulations.
Table 1 provides embodiment 1-16 and comparative example 1-4 parameter and the performance test results.
Finally the performance test results to embodiment 1-16 and comparative example 1-4 are analyzed.
（1）XRD diffraction spectrograms and SEM image analysis
Fig. 1 is the XRD spectrum of the composite doping modification positive electrode active materials of the gained of embodiment 1.Number in Fig. 1 and table 1
According to understanding, the position of the diffraction maximum of the composite doping modification positive electrode active materials obtained by embodiment 1-8 and relative intensity with mark
Quasi- JCPDS cards coincide, and it contains most strong diffraction maximum（311）With the characteristic peak of inverse spinel：Weak peak（111）With secondary strong peak
（220）.The peak type of each diffraction maximum is more sharp in Fig. 1, most strong diffraction maximum（311）Peak intensity can reach 4000, and respectively spread out
Penetrate peak not divide, the crystal formation of the composite doping modification material obtained by explanation is more perfect.Each diffraction maximum is uniformly single in Fig. 1,
There is no other impurity peaks, the composite doping modification positive electrode active materials obtained by explanation are the inverse spinel structure of single crystalline phase.Phase
For embodiment 1-8 XRD diffracting spectrums, the weak peak of the composite doping modification positive electrode active materials obtained by embodiment 9-16
（111）With secondary strong peak（220）2 θ become much larger, the relative intensity at peak is also stronger, more sharp, illustrates obtained by embodiment 9-16
Composite doping modification positive electrode active materials have the inverse spinel structure of more perfect single crystalline phase.And obtained by comparative example 1-4
Positive electrode active materials or composite doping modification positive electrode active materials weak peak（111）With secondary strong peak（220）2 θ to smaller
Direction is migrated, and the relative intensity at peak is also weaker, illustrates the positive electrode active materials or composite doping modification positive pole obtained by comparative example 1-4
Although active material is also inverse spinel structure, but crystal formation and imperfect.
Fig. 2 is the SEM image of the composite doping modification positive electrode active materials of the gained of embodiment 1（7000 times of amplification）.From Fig. 2
In as can be seen that the grain diameter of composite doping modification positive electrode active materials is uniform, surface is smooth, be closely aligned between particle
Together, and the reunion mode of particle is changed into being connected with each other from simple accumulation, so the combination between particle can be made even closer
And microstructure is formed, so as to be conducive to the insertion and abjection of lithium ion, and then lift composite doping modification positive-active material
The tap density and chemical property of material.
（2）The charge-discharge test analysis of 2032 type button cells
Fig. 3 is first charge-discharge curve map of the 2032 type button cells of the gained of embodiment 1 under 0.1C, and Fig. 4 is implementation
First charge-discharge specific capacity of the 2032 type button cells of the gained of example 1 under 0.1C is to the differential curve figure of charging/discharging voltage, Fig. 5
First electric discharge of the 2032 type button cells of 2032 type button cells and the gained of comparative example 1 for the gained of embodiment 1 under 0.1C
Curve map, Fig. 6 is that 2032 type button cells of the gained of embodiment 1 and 2032 type button cells of the gained of comparative example 1 exist stage by stage
Different multiplying（0.1C、0.2C、0.5C、1.0C）Under cyclic curve figure.
As can be seen that the composite doping modification positive-active of the present invention from embodiment 1-16 and comparative example 1-3 contrast
Material LirQ1-xMxVO4-yNyCrystal formation it is more perfect, therefore with higher electric discharge working voltage platform first, it is higher first
Specific discharge capacity and higher coulombic efficiency first, at the same 80 times circulation after capability retention it is also higher, this be mainly because
Radius for the cation M of doping is moderate, with bigger octahedra potential energy, can part substituted metal atom Q, so as to so that
The lattice of composite doping modification positive electrode active materials diminishes, and structure tends towards stability, and then improves composite doping modification positive-active
The chemical property of material.And the anion N adulterated can partly replace O atom, so as to be effectively increased composite doping modification
The electron acceptor of positive electrode active materials, makes to form vacancy volume increase in part oxygen defect, structure cell in crystal, is conducive to lithium ion
Insertion and abjection.
As can be seen that the inverse spinel material handled by composite doping modification from embodiment 1 and comparative example 1-3 contrast
Material（Embodiment 1）Relative to no pure inverse spinel material Jing Guo any doping treatment（Comparative example 1）Change with single ion doping
Property processing inverse spinel material（Comparative example 2 and comparative example 3）, its structure and shape characteristic be more perfect, chemical property
More excellent, working voltage platform of discharging first can raise about 0.2V, and first discharge specific capacity can raise about 5mAh/g, first storehouse
Human relations efficiency can raise about 16%, and the capability retention after 80 circulations can raise about 11%.
As can be seen that using the composite mixed of the sol-gal process synthesis optimized from the contrast of embodiment 1 and comparative example 4
Modified positive electrode active materials have more preferable chemical property, and this is due to that the former with the addition of base operation before calcination, can be protected
The effective supply of the air capacity in the generating process of composite doping modification positive electrode active materials is demonstrate,proved, while making the composite mixed of gained
Modified positive electrode active materials are finer and close, and structure is more stablized；Tempering operation calcine simultaneously after can make what is finalized the design almost to answer
Doping vario-property positive electrode active materials effective temperature-reducing is closed, crystal formation is more stablized and perfect, therefore there can be more preferable electrochemistry
Energy.
In summary, the Stability Analysis of Structures and pattern of composite doping modification positive electrode active materials of the invention are good, using this
The lithium ion battery of the composite doping modification positive electrode active materials of invention has superior chemical property.
Claims (13)
1. a kind of composite doping modification positive electrode active materials, it is characterised in that the composite doping modification positive electrode active materials
Formula is LirQ1-xMxVO4-yNy, wherein, M, N are doped chemical, and Q is one kind in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, and M is
At least one of Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, Zr, La, Ti, Ca, Ba, B, Si, N be F, Cl, Br, I at least
One kind, 0.6<R≤1.05,0<X≤0.25,0 ＜ y≤0.30, and Q and M differ；
LirQ1-xMxVO4-yNyFor space group Fd-3m (Oh 7), Li atoms are in the space of octahedral coordination, and V atoms are in tetrahedron
The space of coordination, the position shared by Li atoms, metallic atom Q and doped chemical M is (16d, 1/2,1/2,1/2), V atoms institute
The position accounted for is (8a, 1/4,1/4,1/4), and O atom and the position shared by doped chemical N are (32e, x, x, x)；
The XRD diffracting spectrums of the composite doping modification positive electrode active materials include most strong diffraction maximum (311) and inverse spinel
Characteristic peak：Weak peak (111) and time strong peak (220).
2. composite doping modification positive electrode active materials according to claim 1, it is characterised in that
The metallic element Q is one kind in Co, Ni, Mn, Cr；
The doped chemical M is at least one of Cr, Al, Fe, Zr, La；
The doped chemical N is at least one of F, Cl, Br.
3. composite doping modification positive electrode active materials according to claim 1, it is characterised 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, it is characterised in that the composite doping modification
The charging/discharging voltage scope of positive electrode active materials is 2.0V~5.5V.
5. composite doping modification positive electrode active materials according to claim 4, it is characterised in that the composite doping modification
The charging/discharging voltage scope of positive electrode active materials is 2.5V~5.0V.
6. a kind of preparation method of composite doping modification positive electrode active materials, for preparing any one of claim 1-5
Composite doping modification positive electrode active materials, including 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 be Co, Ni,
One kind in Mn, Cr, Al, Mg, Fe, Cu, M is in Co, Ni, Mn, Cr, Al, Mg, Fe, Cu, Zr, La, Ti, Ca, Ba, B, Si
At least one, N differs at least one of F, Cl, Br, I, and Q and M；
(3) mixed solution obtained by step (2) is slowly added into the ligand solution obtained by step (1), and shape under agitation
Into emulsion；
(4) by the emulsion obtained by step (3) at 60 DEG C~100 DEG C heating water bath, evaporate moisture, and be stirred continuously, obtain
Wet gel；
(5) wet gel obtained by step (4) is dried in vacuo at 100 DEG C~150 DEG C, obtains xerogel；
(6) by the pre-burning at 400 DEG C~600 DEG C of the xerogel obtained by step (5), precursor is obtained；
(7) precursor obtained by step (6) is naturally cooled into room temperature, grind into powder and base is made in ball mill afterwards
Body；
(8) base substrate obtained by step (7) is calcined at 600 DEG C~1200 DEG C, naturally cools to after room temperature and ground in ball mill
Clay into power；
(9) powder obtained by step (8) is tempered at 100 DEG C~400 DEG C, obtains composite doping modification positive electrode active materials,
The formula of the composite doping modification positive electrode active materials is LirQ1-xMxVO4-yNy, wherein, 0.6<R≤1.05,0<X≤0.25,
0 ＜ y≤0.30；
LirQ1-xMxVO4-yNyFor space group Fd-3m (Oh 7), Li atoms are in the space of octahedral coordination, and V atoms are in tetrahedron
The space of coordination, the position shared by Li atoms, metallic atom Q and doped chemical M is (16d, 1/2,1/2,1/2), V atoms institute
The position accounted for is (8a, 1/4,1/4,1/4), and O atom and the position shared by doped chemical N are (32e, x, x, x)；
The XRD diffracting spectrums of the composite doping modification positive electrode active materials include most strong diffraction maximum (311) and inverse spinel
Characteristic peak：Weak peak (111) and time strong peak (220).
7. the preparation method of composite doping modification positive electrode according to claim 6, it is characterised in that in step (1)
In, the part is one kind in oxalic acid, citric acid, tartaric acid, ethylenediamine tetra-acetic acid, ethylene glycol, acetylacetone,2,4-pentanedione, hydrogen peroxide.
8. the preparation method of composite doping modification positive electrode according to claim 7, it is characterised in that in step (1)
In, the part is oxalic acid.
9. the preparation method of composite doping modification positive electrode active materials according to claim 6, it is characterised in that in step
(2) in, the Li salt, Q salt, M salt, V salt, N salt formation mixed solution in Li ions, Q ions, M ions, V ions, N from
The mol ratio of son is 1.02r:(1-x):x:1:Y, wherein 0.6<R≤1.05,0<X≤0.25,0<y≤0.30.
10. the preparation method of composite doping modification positive electrode active materials according to claim 9, it is characterised in that 0.8<r
≤ 1.02,0.01<X≤0.22,0.02<y≤0.25.
11. the preparation method of composite doping modification positive electrode active materials according to claim 6, it is characterised in that described
Li salt, Q salt, M salt, V salt, N salt formation mixed solution in Li ions, Q ions, M ions, the mole sum of V ions with
The ratio between mole of part is 1:(1~3).
12. the preparation method of composite doping modification positive electrode active materials according to claim 11, it is characterised in that described
Li salt, Q salt, M salt, V salt, N salt formation mixed solution in Li ions, Q ions, M ions, the mole sum of V ions with
The ratio between mole of part is 1:2.
13. a kind of lithium ion battery, including：
Anode pole piece, including composite doping modification positive electrode active materials；
Cathode pole piece；
Barrier film, is interval between anode pole piece and cathode pole piece；And
Electrolyte；
Characterized in that, the composite doping modification positive electrode active materials are compound mixing any one of claim 1-5
Miscellaneous modified positive electrode active materials.
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| 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 |
| 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 |
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| 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 |
| CN113830830B (en) * | 2021-09-16 | 2023-03-31 | 陕西理工大学 | Flake (NH) with iron and boron codope 4 ) 2 V 4 O 9 Method for producing materials |
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