CN103247796B - Lithium ion battery more crystalline phase positive electrodes and preparation method thereof - Google Patents
Lithium ion battery more crystalline phase positive electrodes and preparation method thereof Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910013733 LiCo Inorganic materials 0.000 claims abstract description 12
- 239000011572 manganese Substances 0.000 claims description 70
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 229910012820 LiCoO Inorganic materials 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 229910012817 LiCoNiO2 Inorganic materials 0.000 claims description 4
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 239000002356 single layer Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 17
- 229910017052 cobalt Inorganic materials 0.000 description 16
- 239000010941 cobalt Substances 0.000 description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 16
- 229910052744 lithium Inorganic materials 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 229910032387 LiCoO2 Inorganic materials 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 230000008859 change Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910052596 spinel Inorganic materials 0.000 description 9
- 239000011029 spinel Substances 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 5
- 230000002427 irreversible effect Effects 0.000 description 5
- 241001274961 Rubus repens Species 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910003289 NiMn Inorganic materials 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910012923 LiCoO2In Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- -1 wherein Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
By the lithium ion battery that the hexagoinal lattice of stratiform and the cubic lattice of spinelle shape form it is LiCo with more crystalline phase positive electrodes, its structural formula the invention discloses a kind of lattice structure1‑x‑y‑ zMnxNiyAlzO2, wherein, 0 ＜ x≤0.3,0≤y≤0.2,0≤Z≤0.02.Relative to the positive electrode of single layer structure, the more crystalline phase positive electrodes of lithium ion battery of the present invention have preferable structural stability and heat endurance, prominent cycle performance, thermal safety energy and high rate performance.In addition, the invention also discloses a kind of lithium ion battery preparation method of more crystalline phase positive electrodes.
Description
Technical field
The invention belongs to technical field of lithium ion, it is more particularly related to which a kind of lithium ion battery use is more
Crystalline phase positive electrode and preparation method thereof.
Background technology
Lithium ion battery is widely used in various consumer electronics and mobile device, and being at present being capable of commercialized energy
Density highest one kind battery.But mobile device is endless for the demand of energy source and power, current lithium ion battery
Energy density is also far from meeting the needs of smart mobile phone, electric automobile, it is therefore desirable to material, structure design optimized,
Further to improve energy density.
For lithium ion battery, the energy density of positive electrode the energy density of battery is influenceed it is great, therefore, positive pole material
Energy density lifting always academia, the industrial quarters focus of attention of material, wherein, cobalt acid lithium is as commercialized lithium-ion electric
Pond positive electrode is studied most.Cobalt acid lithium is since Sony commercial Li-ion batteries, existing more than 30 years history so far, its
For merits and demerits all it is obvious that advantage is that energy density is high, technique is simple, shortcoming is that heat endurance is poor, gram volume is relatively low.
At present, the modification Main Means for cobalt acid lithium have bulk phase-doped and Surface coating：It is bulk phase-doped by adulterate Mg,
Al elements substitute Co in lattice, play Li+Stable lattice, the effect of improvement circulation during deintercalation；Surface coating is mainly
By in one layer of inorganic matter of Surface coating, to improve the contact interface of cobalt acid lithium and electrolyte, protecting the surface of cobalt acid lithium, playing
Improve the effect of cycle performance, storage performance.
The meeting recurring structure change in charge and discharge process of common cobalt acid lithium, when de- Li degree reaches more than 50%, six sides
Crystal phase structure (O3) can deform upon, until de- Li degree reaches 70% (4.5V or so).This process by bulk phase-doped and
The modified means such as Surface coating are reversible changes.But when de- Li degree is more than 70%, hexagoinal lattice deformation reaches certain
Degree starts to produce monocline crystalline phase (P3), and monoclinic crystal is mutually in metastable state, can be automatically transitioned to irreversible O1 structures, therefore work as
Cobalt acid lithium takes off Li+During more than more than 70%, its cycle performance drastically declines.At present, the application of cobalt acid lithium develops to high voltage,
4.45V(vs.Li+/ Li) cobalt acid lithium have begun to be commercialized, but be still unable to meet demand, it is therefore desirable to develop as early as possible
The cobalt acid lithium of 4.5V use above.
As seen from the above analysis, can not effectively solve cobalt acid by traditional bulk phase-doped and Surface coating means
Lithium is more than the 4.5V structure irreversible change the problem of, because either bulk phase-doped or Surface coating is all without changing cobalt
The structure of sour lithium, supporter is simply added on the basis of cobalt acid lithium original structure, do not produced qualitative change, therefore wanted from basic
It is upper to solve the problems, such as more than 4.5V irreversible transitions, it must just change the structure of cobalt acid lithium, make it in Li+During deintercalation not
By or do not produce P3 phases.
The content of the invention
It is an object of the invention to：A kind of lithium ion battery more crystalline phase positive electrodes and preparation method thereof are provided, to carry
High-lithium ion battery cycle performance under high voltages and security performance.
In order to realize foregoing invention purpose, the invention provides a kind of lithium ion battery more crystalline phase positive electrodes, its knot
Structure formula is LiCo1-x-y-zMnxNiyAlzO2, wherein, 0 ＜ x≤0.3,0≤y≤0.2,0≤Z≤0.02, its lattice structure is by stratiform
Hexagoinal lattice and spinelle shape cubic lattice composition.
The lattice structure of cobalt acid lithium is hexagoinal lattice, and its structures shape will necessarily occur O3 when being charged to more than 4.5V and arrive
P3 arrives O1 irreversible structure change again, and such irreversible structure change is not present in the material with spinel structure, and point is brilliant
Stone structure shares transition metal ions with layer structure, in charge and discharge process, ensures CoO2Structure will not produce can not inversion
Change, ensure the invertibity of structure change.Al elements are mainly distributed on the surface of positive electrode, it is ensured that the contact with electrolyte
The stability at interface, by the improvement of bulk structure and surface texture, the cyclical stability of positive electrode is improved, simultaneously because
In the presence of the spinel structure of three-dimensional, ensure Li+The space of deintercalation, big multiplying power discharging property can also be improved.In addition, because point is brilliant
Stone structure has preferable thermostabilization, can improve the heat endurance of material, ensures the security applied under high voltage.
Mn content can not be too high, otherwise influences whether overall volume output；Ni content influences whether overall knot
Structure, therefore content can not be too high；Al too high levels can influence electron conduction.
Improved as lithium ion battery of the present invention with one kind of more crystalline phase positive electrodes, layered hexagoinal lattice and point
The cubic lattice of spar shape is evenly distributed in body phase.The hexagoinal lattice of stratiform needs the cubic lattice common portion with spinelle shape
Divide transition metal ions, Li is maintained using the stability of spinel structure+The stabilization of layer structure during deintercalation, therefore
The hexagoinal lattice of stratiform and the cubic lattice of spinelle shape are evenly distributed.
Improved as lithium ion battery of the present invention with one kind of more crystalline phase positive electrodes, more crystalline phase positive electrodes are
LiCo0.7Mn0.3O2, wherein the LiCoO of stratiform be present2The LiCo of phase and spinelle shape0.5Mn1.5O4Phase.
Improved as lithium ion battery of the present invention with one kind of more crystalline phase positive electrodes, more crystalline phase positive electrodes are
LiCo0.7Mn0.1Ni0.2O2, wherein the LiCoO of stratiform be present2And LiCoNiO2The LiCo of phase and spinelle shape0.5Mn1.5O4With
LiNi0.5Mn1.5O4Phase.
Improved as lithium ion battery of the present invention with one kind of more crystalline phase positive electrodes, more crystalline phase positive electrodes are
LiCo0.88Mn0.05Ni0.05Al0.02O2, wherein the LiCoO of stratiform be present2And LiCoNiO2Mutually and spinelle shape
LiCo0.5Mn1.5O4And LiNi0.5Mn1.5O4, one layer of Al of Surface coating.
In order to realize foregoing invention purpose, present invention also offers a kind of lithium ion battery, and it includes positive plate, negative pole
Piece, the barrier film being interval between positive/negative plate, and electrolyte, wherein, positive plate contains foregoing lithium ion battery polycrystalline
Phase positive electrode.
In order to realize foregoing invention purpose, the system present invention also offers a kind of lithium ion battery with more crystalline phase positive electrodes
Preparation Method, it comprises the following steps：
1) soluble M n salt or soluble M n salt and soluble Ni salt are dissolved in water, addition complexing agent forms molten
Liquid；
2) soluble Co salt is dissolved in water；
3) LiOH solution and ammoniacal liquor are configured, and is mixed；
4) the three kinds of solution prepared in step 1) to step 3) are sprayed into spray chamber simultaneously, heat drying obtains LiCo1-x- yMnxNiy(OH)2Presoma, sintering obtains lithium ion battery with more crystalline phase positive electrode LiCo at 500~1100 DEG C1-x- yMnxNiyO2, wherein, 0 ＜ x≤0.3,0≤y≤0.2.
Improved, further comprised 5) with one kind of the preparation method of more crystalline phase positive electrodes as lithium ion battery of the present invention
To LiCo1-x-yMnxNiyO2Al claddings are carried out, obtain lithium ion battery with more crystalline phase positive electrode LiCo1-x-y-zMnxNiyAlzO2,
Wherein, the 0 ＜ ＜ of x≤0.3,0≤y≤0.2,0 Z≤0.02.
It is equal that the inventive method is by being atomized, quick-drying mode will contain NiMn presomas, presoma containing Co and LiOH
Even mixes, wherein, the mode of atomization can be mixed Material control in nanoscale, and quick-drying mode makes
Obtaining three kinds of liquid phases will not mix, therefore dried solid powder is presoma containing NiMn, presoma containing Co and LiOH
Homogeneous solid mixture, when the hexagonal crystal phase during sintering containing Co and the spinelle cube crystalline phase containing NiMn are being formed
It will not produce and influence each other, therefore the structure that hexagonal structure and spinel structure uniformly coexist can be formed.
Improved as lithium ion battery of the present invention with one kind of the preparation method of more crystalline phase positive electrodes, in step 1), institute
It is ammonium citrate or the ammonium of ethylenediamine tetra-acetic acid two to state complexing agent.
Improved as lithium ion battery of the present invention with one kind of the preparation method of more crystalline phase positive electrodes, in step 1), institute
State that soluble M n salt is manganese nitrate or manganese acetate, soluble Ni salt are nickel nitrate or nickel acetate；In step 2), the soluble Co
Salt is cobalt nitrate or cobalt acetate.
Lithium ion battery of the present invention is with the advantages of preparation method of more crystalline phase positive electrodes：Will not by way of atomization
The material of jljl phase is mixed in Nano grade, is then sintered, and reaches stratiform hexagonal crystal phase and spinelle shape cube crystalline phase is equal
The even purpose for being distributed in material body phase, finally carries out Surface coating, can improve surface texture.
Brief description of the drawings
Below in conjunction with the drawings and specific embodiments, to lithium ion battery of the present invention more crystalline phase positive electrodes and its preparation side
Method is described in detail, wherein：
Fig. 1 is LiCo0.7Mn0.3O2With LiCoO2XRD, it can be seen from the figure that LiCo0.7Mn0.3O2With layer structure
With the characteristic peak of spinel structure.
Fig. 2 is LiCo0.7Mn0.3O2With LiCoO2In 4.6V DSC figure, it can be seen from the figure that LiCo0.7Mn0.3O2Tool
There is the characteristic peak of layer structure and spinel structure.
Fig. 3 is LiCo0.7Mn0.3O2With LiCoO2At 25 DEG C, 3.0~4.6V in button cell, 0.5C/0.5C discharge and recharges
Cyclic curve.
Fig. 4 is LiCo0.7Mn0.1Ni0.2O2With LiCoO225 DEG C, 3.0~4.6V in button cell, 0.5C/0.5C charge and discharges
The cyclic curve of electricity.
Fig. 5 is LiCo0.88Mn0.05Ni0.05Al0.02O2Using traditional method of modifying (single layer structure) and using the present invention
Method (layer structure and spinel structure coexist) is 25 DEG C, 3.0~4.5V in full battery, the cyclic curve of 1C/1C discharge and recharges.
Embodiment
In order that goal of the invention, technical scheme and the advantageous effects of the present invention become apparent from, below in conjunction with accompanying drawing and
Embodiment, the present invention is described in more detail.It should be appreciated that the embodiment described in this specification is merely to explain
The present invention, it is not intended to limit the present invention.
Embodiment 1
Manganese nitrate is dissolved in water, adds ammonium citrate, stir the solution to form that Mn concentration is 1mol/L, its
In, mol ratio Mn：NH4 +=1：1；Cobalt acetate is dissolved in water to the solution to form 1mol/L；Configure 1mol/L LiOH and ammonia
The aqueous solution；Three of the above solution is pressed into Mn：Co：Li mol ratio is 0.3：0.7：1 at the uniform velocity sprays into spray chamber simultaneously, and atomization is formed
Dewdrop in 10~500nm, heat drying obtains LiCo at a temperature of 200 DEG C0.7Mn0.3(OH)3Presoma, enter at 500 DEG C
Row sintering obtains LiCo0.7Mn0.3O2。
Table 1 is LiCo0.7Mn0.3O2With LiCoO2Gram volume contrast under different multiplying, from table 1 it follows that because Mn
Instead of part Co, LiCo0.7Mn0.3O2In 0.2C gram volumes compared with LiCoO2It is low, still, when discharge-rate increases to 2C,
LiCo0.7Mn0.3O2Gram volume compare LiCoO2Gram volume it is high, illustrate LiCo0.7Mn0.3O2With preferable high rate performance.
The LiCo of table 10.7Mn0.3O2With LiCoO2Gram volume under different multiplying
Fig. 1 is LiCo0.7Mn0.3O2With LiCoO2XRD, as can be seen from the figure LiCo0.7Mn0.3O2There is point simultaneously
The characteristic peak of spinel structure and layer structure.
Fig. 2 is LiCo0.7Mn0.3O2With LiCoO2The DSC comparison diagrams in 4.6V, as can be seen from the figure LiCo0.7Mn0.3O2
Thermal runaway temperature compare LiCoO2It is high about 50 degree, and thermal discharge is smaller, illustrates that the presence of spinel structure significantly improves stratiform
The heat endurance of structure cobalt acid lithium.
Fig. 3 is LiCo0.7Mn0.3O2With LiCoO2At 25 DEG C, 3.0~4.6V, the cyclic curve figure of 0.5C/0.5C discharge and recharges,
As can be seen from the figure LiCo0.7Mn0.3O2With preferable cycle performance.
Embodiment 2
Manganese acetate and nickel nitrate are pressed into Mn：Ni mol ratios are 1：2 are dissolved in water, and add the ammonium of ethylenediamine tetra-acetic acid two, stir
The solution for being formed uniformly that Mn concentration is 1mol/L is mixed, wherein, mol ratio Mn：Ni：NH4 +=1：2：3；Cobalt nitrate is dissolved in water
Form 1mol/L solution；Configure 1mol/L LiOH and ammonia spirit；Three of the above solution is pressed into Mn：Ni：Co：Li mole
Than for 0.1：0.2：0.7：1 at the uniform velocity sprays into spray chamber simultaneously, is atomized the dewdrop of formation in 10~500nm, and at a temperature of 200 DEG C
Heat drying obtains LiCo0.7Mn0.1Ni0.2(OH)3Presoma, then it is sintered to obtain at a temperature of 1100 DEG C
LiCo0.7Mn0.1Ni0.2O2。
Fig. 4 is LiCo0.7Mn0.1Ni0.2O2With LiCoO2At 25 DEG C, 3.0~4.6V, the circulation of 0.5C/0.5C discharge and recharges is bent
Line chart, it can be seen that LiCo0.7Mn0.1Ni0.2O2With preferable cycle performance.
Embodiment 3
By manganese nitrate and nickel acetate Mn in molar ratio：Ni=1：1 is dissolved in water, and adds ammonium citrate, stir shape
Into the solution that Mn concentration is 1mol/L, wherein, mol ratio Mn：Ni：NH4 +=1：1：2；Cobalt nitrate is dissolved in water to be formed
1mol/L solution；Configure 1mol/L LiOH and ammonia spirit；Three of the above solution is pressed into Mn：Ni：Co：Li mol ratio is
0.05：0.05：0.9：1 at the uniform velocity sprays into spray chamber simultaneously, is atomized the dewdrop of formation in 10~500nm, and adds at a temperature of 200 DEG C
Heated drying obtains LiCo0.9Mn0.05Ni0.05(OH)3Presoma；It is sintered to obtain layer structure and spinelle knot at 900 DEG C
The LiCo that structure coexists0.9Mn0.05Ni0.05O2；By LiCo0.9Mn0.05Ni0.05O2With Al (OH)3Li in molar ratio：Al=1：0.02 is mixed
Close uniformly, and sinter 2h at 600 DEG C and obtain Surface coating Al LiCo0.88Mn0.05Ni0.05Al0.02O2。
By LiCo0.88Mn0.05Ni0.05Al0.02O2Anode sizing agent is obtained with being stirred together with conductive carbon, PVDF, by positive pole
Slurry is coated uniformly on Al paper tinsels and positive plate is made；Positive plate is wound into battery core with barrier film, negative plate, injects electrolyte, and
Lithium ion battery is obtained by chemical conversion.
Comparative example 1
Cobalt nitrate is dissolved in water to the solution to form 1mol/L；Configure 1mol/L LiOH and ammonia spirit；By more than
Two kinds of solution press Co：Li mol ratio is 1：1 at the uniform velocity sprays into spray chamber simultaneously, is atomized the dewdrop of formation in 10~500nm, and
200 DEG C of heat dryings obtain LiCo (OH)3Presoma, it is sintered to obtain LiCoO at 500 DEG C2。
Comparative example 2
According to the conventional method, by Co3O4、NiCO3、MnCO3、Li2CO3Li in molar ratio：Co：Ni：Mn=1：0.9：
0.05：0.05 is well mixed, and sintering obtains LiCo0.9Mn0.05Ni0.05O2；By LiCo0.9Mn0.05Ni0.05O2With Al (OH)3Massage
You compare Li：Al=1：0.02 is well mixed, and sinters at 600 DEG C 2h and obtain Surface coating Al only layer structure
LiCo0.88Mn0.05Ni0.05Al0.02O2。
Method according to embodiment 3 prepares lithium ion battery.
Fig. 5 be comparative example 2 and the lithium ion battery of the embodiment of the present invention 3 at 25 DEG C, 3.0~4.5V, 1C/1C charge and discharges
The cyclic curve comparison diagram of electricity, can be clearly seen that from figure, have the hexagoinal lattice and spinelle of stratiform using the present invention
The LiCo of the cubic lattice of shape0.88Mn0.05Ni0.05Al0.02O2The cycle performance of lithium ion battery be substantially better than in the prior art
The only LiCo of layer structure0.88Mn0.05Ni0.05Al0.02O2Lithium ion battery cycle performance, it is more preferable to show that the present invention has
High voltage cycle performance.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula carries out appropriate change and modification.Therefore, the invention is not limited in embodiment disclosed and described above, to this
Some modifications and changes of invention should also be as falling into the scope of the claims of the present invention.In addition, although this specification
In used some specific terms, but these terms are merely for convenience of description, do not form any restrictions to the present invention.
Claims (9)
- A kind of 1. more crystalline phase positive electrodes of lithium ion battery, it is characterised in that the more crystalline phase positive pole materials of the lithium ion battery The structural formula of material is LiCo1-x-y-zMnxNiyAlzO2, wherein, 0 ＜ x≤0.3,0≤y≤0.2,0≤Z≤0.02, its lattice structure It is made up of the hexagoinal lattice of stratiform and the cubic lattice of spinelle shape；Layered hexagoinal lattice and the cubic crystal of spinelle shape Lattice are evenly distributed in body phase, the hexagoinal lattice of stratiform and the cubic lattice common sparing transition metal ions of spinelle shape.
- 2. the more crystalline phase positive electrodes of lithium ion battery according to claim 1, it is characterised in that more crystalline phase positive poles Material is LiCo0.7Mn0.3O2, wherein the LiCoO of stratiform be present2The LiCo of phase and spinelle shape0.5Mn1.5O4Phase.
- 3. the more crystalline phase positive electrodes of lithium ion battery according to claim 1, it is characterised in that more crystalline phase positive poles Material is LiCo0.7Mn0.1Ni0.2O2, wherein the LiCoO of stratiform be present2And LiCoNiO2Mutually and spinelle shape LiCo0.5Mn1.5O4And LiNi0.5Mn1.5O4Phase.
- 4. the more crystalline phase positive electrodes of lithium ion battery according to claim 1, it is characterised in that more crystalline phase positive poles Material is LiCo0.88Mn0.05Ni0.05Al0.02O2, wherein the LiCoO of stratiform be present2And LiCoNiO2Mutually and spinelle shape LiCo0.5Mn1.5O4And LiNi0.5Mn1.5O4, one layer of Al of Surface coating.
- 5. a kind of lithium ion battery, it includes positive plate, negative plate, the barrier film being interval between positive/negative plate, and electrolysis Liquid, it is characterised in that the positive plate contains the more crystalline phase positive poles of lithium ion battery any one of Claims 1-4 Material.
- 6. a kind of lithium ion battery preparation method of more crystalline phase positive electrodes, it is characterised in that comprise the following steps：1) soluble M n salt or soluble M n salt and soluble Ni salt are dissolved in water, add complexing agent and form solution；2) soluble Co salt is dissolved in water；3) LiOH solution and ammoniacal liquor are configured, and is mixed；4) the three kinds of solution prepared in step 1) to step 3) are sprayed into spray chamber simultaneously, heat drying obtains LiCo1-x-yMnxNiy (OH)2Presoma, sintering obtains the cubic lattice composition of the hexagoinal lattice and spinelle shape with stratiform at 500~1100 DEG C Lithium ion battery with more crystalline phase positive electrode LiCo1-x-yMnxNiyO2, wherein, 0 ＜ x≤0.3,0≤y≤0.2.
- 7. preparation method according to claim 6, further comprise 5) to LiCo1-x-yMnxNiyO2Al claddings are carried out, are obtained The more crystalline phase positive electrode LiCo of lithium ion battery1-x-y-zMnxNiyAlzO2, wherein, the 0 ＜ ＜ of x≤0.3,0≤y≤0.2,0 Z≤ 0.02。
- 8. preparation method according to claim 6, it is characterised in that in step 1), the complexing agent be ammonium citrate or The ammonium of ethylenediamine tetra-acetic acid two.
- 9. preparation method according to claim 6, it is characterised in that in step 1), the soluble M n salt is manganese nitrate Or manganese acetate, soluble Ni salt are nickel nitrate or nickel acetate；In step 2), the soluble Co salt is cobalt nitrate or cobalt acetate.
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| CN103500827B (en) * | 2013-10-11 | 2017-05-24 | 宁德新能源科技有限公司 | Lithium ion battery and multi-element positive material thereof as well as preparation method of multi-element positive material |
| CN106935797B (en) * | 2015-12-31 | 2019-02-26 | 北京当升材料科技股份有限公司 | A kind of lithium ion battery presoma, positive electrode, lithium ion cell positive and lithium ion battery |
| CN108123109B (en) * | 2016-11-28 | 2020-09-29 | 华为技术有限公司 | Lithium cobalt oxide cathode material and preparation method thereof, and lithium ion secondary battery |
| JP6966308B2 (en) * | 2017-12-11 | 2021-11-10 | トヨタ自動車株式会社 | Positive active material for lithium-ion batteries and their manufacturing methods, lithium-ion batteries, and lithium-ion battery systems |
| CN109088067B (en) * | 2018-09-29 | 2020-08-07 | 广东邦普循环科技有限公司 | Preparation method of low-cobalt-doped spinel-layered-structure lithium nickel manganese oxide two-phase composite positive electrode material |
| CN111326783B (en) | 2018-12-14 | 2021-07-13 | 宁德时代新能源科技股份有限公司 | Lithium Ion Battery |
| CN109809497B (en) * | 2019-01-17 | 2021-10-01 | 合肥国轩高科动力能源有限公司 | A method for synthesizing LiCoO2 powder by ultrasonic spray calcination and its application |
| CN114883555B (en) * | 2022-06-09 | 2024-01-30 | 贵州高点科技有限公司 | Multiphase manganese material, preparation method thereof, positive plate and secondary battery |
| CN119660827B (en) * | 2025-02-21 | 2025-05-13 | 东莞市云帆电子科技有限公司 | Cobalt-free lithium-rich manganese-based oxide material for lithium-ion batteries and preparation method thereof |
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