CN102969494B - Lithium nickel manganese oxide composite material, its preparation method and lithium ion battery - Google Patents
Lithium nickel manganese oxide composite material, its preparation method and lithium ion battery Download PDFInfo
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- CN102969494B CN102969494B CN201110258108.7A CN201110258108A CN102969494B CN 102969494 B CN102969494 B CN 102969494B CN 201110258108 A CN201110258108 A CN 201110258108A CN 102969494 B CN102969494 B CN 102969494B
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- composite material
- manganese oxide
- positive active
- lithium nickel
- active material
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- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 121
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- 239000007774 positive electrode material Substances 0.000 claims description 87
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 66
- 229910052782 aluminium Inorganic materials 0.000 claims description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 42
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 37
- 239000004411 aluminium Substances 0.000 claims description 36
- 238000003475 lamination Methods 0.000 claims description 36
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 27
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- 239000010452 phosphate Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000014759 maintenance of location Effects 0.000 claims description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000013543 active substance Substances 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 description 42
- 239000011572 manganese Substances 0.000 description 40
- 239000000243 solution Substances 0.000 description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 33
- 239000002253 acid Substances 0.000 description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 229910017052 cobalt Inorganic materials 0.000 description 28
- 239000010941 cobalt Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 24
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 19
- 229910052759 nickel Inorganic materials 0.000 description 19
- 229910052748 manganese Inorganic materials 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 15
- 238000001354 calcination Methods 0.000 description 10
- 239000011247 coating layer Substances 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- -1 phosphate anion Chemical class 0.000 description 10
- 229910017119 AlPO Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 150000003016 phosphoric acids Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000004087 circulation Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 229910013716 LiNi Inorganic materials 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001868 cobalt Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- AJJBCQJUDJPUJP-UHFFFAOYSA-K aluminum cobalt(2+) phosphate Chemical compound P(=O)([O-])([O-])[O-].[Al+3].[Co+2] AJJBCQJUDJPUJP-UHFFFAOYSA-K 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical group [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000010189 synthetic method Methods 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a lithium nickel manganese oxide composite material, which comprises anode active substance particles and aluminum phosphate layers coated on the surface of the anode active substance particles, an anode active substance particle material is expressed by a chemical formula of LixNi0.5aMn1.5-y-bMaNbO4, wherein x is greater than or equal to 0.1 and less than or equal to 1.1, y is greater than or equal to 0 and less than 1.5, a-y is greater than or equal to 0 and less than 0.5, M and N are one or more selected from alkali metal elements, alkali earth metal, 13th element, 14th element, transitional element and rare earth element. The invention also relates to a preparation method of the lithium nickel manganese oxide composite material and a lithium ion battery.
Description
Technical field
The present invention relates to a kind of lithium nickel manganese oxide composite material and preparation method thereof, and lithium ion battery.
Background technology
Adopting other material to be formed to the particle surface of active substance of lithium ion battery anode coated, is the common method of in prior art, positive active material being carried out to modification.Such as, effectively can solve the lower problem of LiFePO4 conductivity at the particle surface of LiFePO4 coated one deck carbon, make the LiFePO4 being coated with carbon-coating have good conductivity.In addition, prior art shows, and the thermal stability that can improve lithium ion cell positive at cobalt acid lithium or the coated aluminum phosphate of other positive active material particle surface (refers to document " Correlation between AlPO
4nanoparticle coating thickness on LiCoO
2cathode and thermal stablility " J.Cho, Electrochimica Acta 48 (2003) 2807-2811 and the patent No. be 7,326, the United States Patent (USP) of 498).
First prepare the dispersion liquid that aluminum phosphate Granular composite formed in water by the method for aluminum phosphate clad anode active material in prior art, and positive active material particle is added in the dispersion liquid of this aluminum phosphate particle prepared, make aluminum phosphate granular absorption at positive active material large particle surface by the effect of absorption, again by the water evaporate to dryness in dispersion liquid, and heat treatment at 700 DEG C, form the positive active material that surface has aluminum phosphate particle.
But, because aluminum phosphate is water insoluble, reunion may be formed when aluminum phosphate particle disperses in water, and when a large amount of positive active material is added in aluminum phosphate dispersion liquid, the positive active material first added adsorbs a large amount of aluminum phosphate particle, after the positive active material particle that adds then may adsorb less than enough aluminum phosphate particles.Refer to Figure 17, even if can be good at coated, said method determines that this product 20 is that aluminum phosphate is surperficial at positive active material bulky grain 24 with the fractions distribution of granule 22 from microcosmic, the not even aluminum phosphate material layer of one deck.Therefore, the aluminum phosphate coating layer formed on positive active material surface by said method is even not, cannot ensure that each positive active material surface all can uniform coated one deck aluminum phosphate, thus make the cycle performance of lithium ion battery of this positive active material of application bad, make the method be difficult to heavy industrialization application.
Summary of the invention
In view of this, necessaryly provide a kind of method that can form even aluminum phosphate coating layer at Li, Ni, Mn oxide particle surface, and there is the lithium nickel manganese oxide composite material of this aluminum phosphate coating layer, and apply the lithium ion battery of this lithium nickel manganese oxide composite material.
A kind of lithium nickel manganese oxide composite material, it phosphoric acid aluminium lamination comprising positive active material particle and be coated on this positive active material particle surface, the material of this positive active material particle is by chemical formula Li
xni
0.5+y-amn
1.5-y-bm
an
bo
4represent, wherein 0.1≤x≤1.1,0≤y<1.5,0≤a-y<0.5, and 0≤b+y<1.5, M and N are one or more in alkali metal, alkali earth metal, the 13rd race's element, the 14th race's element, transition element and rare earth element.
A preparation method for lithium nickel manganese oxide composite material, it comprises: provide aluminum nitrate solution; Add in this aluminum nitrate solution by positive active material particle to be covered, form mixture, the material of this positive active material particle is by chemical formula Li
xni
0.5+y-amn
1.5-y-bm
an
bo
4represent, wherein 0.1≤x≤1.1,0≤y<1.5,0≤a-y<0.5, and 0≤b+y<1.5, M and N are one or more in alkali metal, alkali earth metal, the 13rd race's element, the 14th race's element, transition element and rare earth element; Phosphate solution is added this mixture to react, form phosphoric acid aluminium lamination at this positive active material particle surface; And this surface of heat treatment has the positive active material particle of phosphoric acid aluminium lamination.
A kind of lithium ion battery, it comprises positive pole, and this positive pole comprises above-mentioned lithium nickel manganese oxide composite material.
Compared to prior art, the absorption that present invention, avoiding due to solid mixing generation is uneven, causes the phenomenon of the coated inequality of aluminum phosphate, is applicable to heavy industrialization application.In addition, the present invention can generate a layer thickness evenly and continuous print phosphoric acid aluminium lamination at positive active material particle surface, but not by aluminum phosphate particle packing at positive active material particle surface, therefore has better chemical property.
Accompanying drawing explanation
Fig. 1 is the structural representation of embodiment of the present invention aluminum phosphate clad anode active material.
Fig. 2 is the stereoscan photograph of embodiment of the present invention aluminum phosphate coated cobalt acid lithium.
Fig. 3 is the transmission electron microscope photo of embodiment of the present invention aluminum phosphate coated cobalt acid lithium.
Fig. 4 be embodiment of the present invention aluminum phosphate coated cobalt acid lithium cycle performance test curve.
Fig. 5 is the stereoscan photograph of the aluminum phosphate coated cobalt acid lithium of the magnification at high multiple of contrast experiment.
Fig. 6 is the stereoscan photograph of the aluminum phosphate coated cobalt acid lithium that the low power of contrast experiment is amplified.
Fig. 7 is the cycle performance test curve of the coated positive active material of the aluminum phosphate of contrast experiment.
Fig. 8 is the cycle performance test curve of the not coated Li, Ni, Mn oxide of the coated Li, Ni, Mn oxide of embodiment of the present invention aluminum phosphate and contrast experiment.
The stereoscan photograph of the spherical powder particle before Fig. 9 heat treatment that to be the embodiment of the present invention synthesized by crystallization control method.
Figure 10 is the stereoscan photograph of the spherical lithium nickel Mn oxide that the embodiment of the present invention is synthesized by crystallization control method.
Figure 11 is the XRD analysis spectrogram of the not coated spherical lithium nickel Mn oxide of the coated spherical lithium nickel Mn oxide of embodiment of the present invention aluminum phosphate and contrast test.
Figure 12 is the transmission electron microscope photo of the coated spherical lithium nickel Mn oxide of embodiment of the present invention aluminum phosphate.
Figure 13 is the lithium ion battery first charge-discharge curve of the not coated spherical lithium nickel Mn oxide of the coated spherical lithium nickel Mn oxide of embodiment of the present invention aluminum phosphate and contrast test.
Figure 14 is the cycle performance curve of lithium ion battery under different multiplying of the not coated spherical lithium nickel Mn oxide of the coated spherical lithium nickel Mn oxide of embodiment of the present invention aluminum phosphate and contrast test.
Figure 15 is the lithium ion battery first charge-discharge curve of the coated spherical lithium nickel Mn oxide of the aluminum phosphate of the different covering amount of the embodiment of the present invention.
Figure 16 is the cycle performance curve of the lithium ion battery of the coated spherical lithium nickel Mn oxide of the aluminum phosphate of the different covering amount of the embodiment of the present invention.
Figure 17 is the structural representation of the aluminum phosphate clad anode active material of prior art.
Main element symbol description
| Anode composite material particle | 10 |
| Positive active material particle | 12 |
| Phosphoric acid aluminium lamination | 14 |
| Product | 20 |
| Granule | 22 |
| Bulky grain | 24 |
Following embodiment will further illustrate the present invention in conjunction with above-mentioned accompanying drawing.
Embodiment
Below in conjunction with the accompanying drawings and the specific embodiments to lithium nickel manganese oxide composite material provided by the invention and preparation method thereof, and lithium ion battery is described in further detail.
Refer to Fig. 1, the embodiment of the present invention provides a kind of anode composite material particle 10, it phosphoric acid aluminium lamination 14 comprising positive active material particle 12 and be coated on this positive active material particle surface.The mass percent of this phosphoric acid aluminium lamination 14 in this anode composite material particle 10 is 0.1% to 3%.The thickness of this phosphoric acid aluminium lamination 14 is preferably 5 nanometer to 20 nanometers.This phosphoric acid aluminium lamination 14 is that in-situ preparation is on this positive active material particle 12 surface.This phosphoric acid aluminium lamination 14 be thickness evenly and continuous print aluminum phosphate material layer.The all surface of this positive active material particle 12 is all covered by this continuous print phosphoric acid aluminium lamination 14.Further, the interface between this phosphoric acid aluminium lamination 14 and this positive active material particle 12 may form interfacial diffusion, and cobalt atom is diffused in this phosphoric acid aluminium lamination 14.
The material of this positive active material particle 12 can be stratiform cobalt acid lithium structure or the spinel lithium manganate structure of mixing nickel, specifically can by chemical formula Li
xco
1-zm
zo
2or Li
xni
0.5+y-amn
1.5-y-bm
an
bo
4represent, wherein 0.1≤x≤1.1,0≤y<1.5,0≤a-y<0.5,0≤b+y<1.5, and 0≤z<1.M and N be all selected from alkali metal, alkali earth metal, the 13rd race's element, the 14th race's element, transition element and rare earth element one or more, preferably, M and N is selected from least one in Cr, Co, V, Ti, Al, Fe, Ga and Mg.Wherein y range preferably from 0≤y<0.1.Particularly, the chemical formula of the material of this positive active material particle 12 can be LiCoO
2or LiNi
0.5mn
1.5o
4.The particle diameter of this positive active material particle 12 is preferably 100 nanometers to 100 micron, is more preferably 1 micron to 20 microns.
The embodiment of the present invention provides a kind of by aluminum phosphate coated lithium ion battery positive active material, and form the method for described anode composite material particle 10, it comprises the following steps:
Step one, provides aluminum nitrate solution;
Step 2, adds positive active material particle to be covered in this aluminum nitrate solution, forms a mixture;
Step 3, adds this mixture and reacts by phosphate solution, make this positive active material particle surface form phosphoric acid aluminium lamination; And
Step 4, this surface of heat treatment has the positive active material particle of phosphoric acid aluminium lamination, obtains anode composite material particle.
This aluminum nitrate solution comprises liquid phase solvent and is dissolved in the aluminum nitrate of this solvent.Be appreciated that this solvent be chosen as can make aluminum nitrate dissociate formed Al
3+solvent.Therefore this solvent is not limited to water, can also be volatile organic solvent, and preferably, this solvent is one or several mixing in ethanol, acetone, dichloroethanes and chloroform.Relative to employing water as solvent, using organic solvent if ethanol is as solvent, positive active material particle and water can be avoided to react positive active material performance is reduced.
In above-mentioned steps two, this positive active material particle is insoluble to this aluminum nitrate solution, and both are solid-liquid mixing, and object adheres to one deck Al at the surface uniform of this positive active material particle
3+.Due to Al
3+exist in the form of an ion, positive active material particle surface can be attached to uniformly, the coated of atom level is formed to this positive active material particle.Further, can control the addition of this positive active material, controlled being made as of the ratio of this positive active material particle and aluminum nitrate solution enables this aluminum nitrate solution cover this positive active material particle surface, makes the mixture obtained be muddy.The object forming muddy mixture mainly forms one deck aluminum phosphate coating layer in order to the addition controlling aluminum nitrate solution is just enough at positive active material particle surface.Particularly, the volume of this aluminum nitrate solution and the volume ratio of this positive active material particle are about 1:10 to 1:40.The particle diameter of this positive active material particle is preferably less than 20 microns.The mass percent that the addition of this aluminum nitrate solution accounts for anode composite material particle by the aluminum phosphate coating layer that needs are formed is determined, preferably, the mass percent of this aluminum phosphate coating layer in this anode composite material particle is 0.1% to 3%.
In above-mentioned steps three, this phosphate solution comprises water as solvent, and is dissolved in the soluble phosphate of this solvent, as phosphoric acid ammonia salt.This phosphoric acid ammonia salt comprises ammonium dihydrogen phosphate (NH
4h
2pO
4), diammonium hydrogen phosphate ((NH
4)
2hPO
4) and triammonium phosphate ((NH
4)
3pO
4) in the mixing of one or more.Containing phosphate anion in this phosphate solution.This phosphate anion can be positive phosphorus acid ion (PO
4 3-), dihydrogen phosphate ions (H
2pO
4 -) and phosphoric acid one hydrogen radical ion (HPO
4 2-) in the mixing of one or more.When this phosphate solution is added to described muddy mixture, this phosphate anion and the Al being attached to positive active material particle surface
3+reaction, thus form the uniform aluminum phosphate precipitation of one deck in positive active material particle surface original position.Preferably, this phosphate solution dropwise can add this muddy mixture, and is stirred, thus makes this phosphate anion and this Al
3+can react uniformly at this positive active material particle surface.With aluminum nitrate solution similarly, the addition of this phosphate solution is determined by the mass percent needing the aluminum phosphate coating layer formed and account for anode composite material particle.
In above-mentioned steps four, this heat treated object is that this aluminum phosphate is better combined in interface with positive active material, forms composite material, and removes the ammonium nitrate of residual solvent and reaction generation.By this heat treatment, may interfacial diffusion be formed at aluminum phosphate and positive active material interface, the metallic atom in positive active material is diffused in this phosphoric acid aluminium lamination.This heat treatment temperature can be 400 DEG C to 800 DEG C.This heat treated time is preferably 0.5 to 2 hour.
Because positive active material particle first joins in aluminum nitrate solution by this method, add in this aluminum nitrate solution again and can react with aluminium ion the phosphate solution generating aluminum phosphate, thus at positive active material particle surface in-situ preparation one deck continuous print phosphoric acid aluminium lamination.Because the aluminum nitrate solution of liquid phase mixes with the positive active material particle of solid phase, aluminium ion can be first made to be coated on this positive active material particle surface uniformly, therefore, the aluminum phosphate precipitation generated by aluminium ion after reaction in-situ also can evenly and continuous print be coated on the whole surface of this positive active particles.With first synthesize aluminum phosphate particle, by suction-operated, aluminum phosphate granular absorption is compared to the mode of positive active material particle surface again, the absorption that this method avoids due to solid mixing generation is uneven, cause coated uneven, the discontinuous or coated incomplete phenomenon of aluminum phosphate, be applicable to heavy industrialization application.In addition, this method can generate the complete thickness of one deck evenly and continuous print phosphoric acid aluminium lamination at positive active material particle surface, but not by aluminum phosphate particle packing at positive active material particle surface.This phosphoric acid aluminium lamination can make ion pass through while the electron transfer between isolated electrolyte and active material, thus complete the embedding of lithium ion and while deviating from, avoiding electrolyte to decompose at higher voltages, therefore make this positive active material can have better battery performance and capacity retention energy at higher voltages.
The embodiment of the present invention specifically adopts said method to prepare described anode composite material particle by aluminum phosphate clad anode active material particle, and is applied in lithium ion battery by this anode composite material particle and carries out performance test.
Embodiment 1: aluminum phosphate-cobalt acid lithium composite material
In the present embodiment, this positive active material particle is cobalt acid lithium particle, and chemical formula is LiCoO
2.This aluminum phosphate-cobalt acid lithium composite material comprises cobalt acid lithium particle and is coated on the phosphoric acid aluminium lamination of this cobalt acid lithium particle surface.
In the preparation of this aluminum phosphate-cobalt acid lithium composite material, this aluminum nitrate solution is the solution that aluminum nitrate is formed in ethanol.The volume of this aluminum nitrate solution is 30 milliliters, and molar concentration is 0.16 mol/L.The addition of this cobalt acid lithium particle is 100g.This phosphate solution is (NH
4)
2hPO
4the aqueous solution.Be respectively 400 DEG C, 500 DEG C and 600 DEG C in heat treatment temperature, the mass percent that phosphoric acid aluminium lamination accounts for gross mass is prepare 3 kinds of aluminum phosphates-cobalt acid lithium composite material particulate samples under the condition of 1%.In addition, be 600 DEG C in heat treatment temperature, the mass percent that phosphoric acid aluminium lamination accounts for gross mass is prepare a kind of aluminum phosphate-cobalt acid lithium composite material sample under the condition of 1.5%.Refer to Fig. 2 and Fig. 3, in the sample obtained, phosphoric acid aluminium lamination is coated on this cobalt acid lithium particle surface uniformly, by high magnification transmission electron microscope observing, clearly can see that this aluminum phosphate covers this cobalt acid lithium particle surface surface with the form of the uniform material layer of thickness.Respectively these 4 kinds of samples are mixed with a certain proportion of conductive agent and binding agent and be coated on anode collection surface and make positive pole, using metal lithium sheet as negative pole, positive pole and negative pole are infiltrated by barrier film interval and with electrolyte and is assembled into lithium ion battery, carry out charge-discharge performance test.In the present embodiment, this conductive agent is acetylene black, and binding agent is Kynoar, and the mass ratio of positive electrode active materials and conductive agent and binding agent is 8:1:1.Barrier film is microporous polypropylene membrane, and electrolyte is 1mol/L LiPF
6/ EC+DEC (1:1) solution.
Be coated with the positive active material particle of aluminum phosphate, because the aluminum phosphate playing coating function improves the surface texture of positive active material particle, de-deficient platform is provided to lithium ion, play the effect on barrier layer simultaneously, tetravalence cobalt ions and electrolyte is effectively suppressed to react, stabilize cobalt acid lithium structure, improve electrochemistry cycle performance.Refer to Fig. 4, above-mentioned 4 kinds of samples are carried out constant current charge-discharge loop test under 0.5C electric current, the cut-ff voltage of this charging is 4.5V, and the cut-ff voltage of electric discharge is 2.7V.Can find from figure, adopt sample prepared by the inventive method, because aluminum phosphate can uniform coated cobalt acid alumina particles, charge at higher voltages and still can have higher capacity and stable capability retention, capability retention after 50 circulations is all more than 90%, and specific capacity is 160mAh/g to 175mAh/g.Further, along with the raising of heat treatment temperature, the capacity of battery increases to some extent.The impact of change on battery capacity of this aluminum phosphate percentage composition is little.
Contrast experiment 1
For the anode composite material particle prepared with the embodiment of the present invention 1 contrasts, prepare another comparative sample with the method for prior art, concrete steps are:
By (NH
4)
2hPO
4the aqueous solution mixes with aluminum nitrate aqueous solution, generates aluminum phosphate particle in water, forms dispersion liquid;
Cobalt acid lithium particle is dropped in this dispersion liquid, makes aluminum phosphate granular absorption at cobalt acid lithium particle surface by the effect of absorption; And
At 600 DEG C, this adsorption of heat treatment has the cobalt acid lithium particle of aluminum phosphate particle, obtains described comparative sample.Refer to Fig. 5 and Fig. 6, in the comparative sample prepared by art methods, aluminum phosphate is that the form of particle is gathered in this cobalt acid lithium particle surface, and aluminum phosphate agglomerate grain, make coated uneven.
By the aluminum phosphate in this comparative sample alternative embodiment 1-cobalt acid lithium composite material, assembled battery under the same conditions as example 1, carries out charge-discharge performance test.In addition also using the cobalt of not coated any material acid lithium particle as positive active material, be assembled into lithium ion battery under the same conditions as example 1, carry out charge-discharge performance test.Above-described embodiment 1 is only positive electrode active materials with the difference of contrast experiment, and other battery condition and test condition are all identical.
Refer to Fig. 7, the circulation volume of this comparative sample and not coated cobalt acid lithium particulate samples then sharply declines, capability retention after 50 circulations is all less than 85%, this is mainly because cobalt acid lithium particles coat is uneven or not coated, when making under high pressure to charge, cobalt acid lithium and electrolyte react and the capacity of battery are reduced.
Embodiment 2: aluminum phosphate-lithium nickel manganese oxide composite material
In the present embodiment, this positive active material particle is the Li, Ni, Mn oxide particle of spinel-type, and chemical formula is LiNi
0.5mn
1.5o
4.This aluminum phosphate-lithium nickel manganese oxide composite material comprises Li, Ni, Mn oxide particle and is coated on the phosphoric acid aluminium lamination of this Li, Ni, Mn oxide particle surface.The preparation method of this aluminum phosphate-lithium nickel manganese oxide composite material is identical with the preparation method of the aluminum phosphate of above-described embodiment 1-cobalt acid lithium composite material particle, heat treatment temperature is chosen as 600 DEG C, difference is only Li, Ni, Mn oxide at the material of positive active material particle, and the mass percent that phosphoric acid aluminium lamination accounts for gross mass is 0.5%.By the aluminum phosphate of this aluminum phosphate-lithium nickel manganese oxide composite material alternative embodiment 1-cobalt acid lithium composite material, be assembled into lithium ion battery under the same conditions as example 1.This lithium ion battery is carried out constant current charge-discharge loop test under 0.2C electric current, and the cut-ff voltage of this charging is 5V, and the cut-ff voltage of electric discharge is 3V, and after 50 circulations, the capability retention of battery is all more than 95%, and specific capacity is about 138mAh/g.In addition, refer to Fig. 8, this lithium ion battery is carried out constant current charge-discharge loop test under 1C electric current, under 1C electric current, after 50 circulations, the capability retention of battery still can reach 95%, and specific capacity is about 132mAh/g.
Contrast experiment 2
By not coated LiNi
0.5mn
1.5o
4particle, as positive active material, is assembled into lithium ion battery under the same conditions as example 1, carries out charge-discharge performance test.The test result of this test result and embodiment 2 contrasts in fig. 8, finds to use this not coated LiNi
0.5mn
1.5o
4particle is about 86% as the capability retention of lithium ion battery rear battery of 50 circulations under 1C electric current of positive active material, and specific capacity is about 118mAh/g.
Embodiment 3: aluminum phosphate-spherical lithium nickel manganese oxide composite material
In the present embodiment, first by crystallization control method synthesizing spherical Li, Ni, Mn oxide, then it is coated to carry out aluminum phosphate to this spherical lithium nickel Mn oxide.The chemical formula of this spherical lithium nickel Mn oxide is LiNi
0.5mn
1.5o
4.This aluminum phosphate-spherical lithium nickel manganese oxide composite material comprises spherical lithium nickel Mn oxide and is coated on the phosphoric acid aluminium lamination on this spherical lithium nickel Mn oxide surface.
The crystallization control synthetic method preparing this spherical lithium nickel Mn oxide comprises the following steps:
Manganese source compound and the nickel source compound of solubility are provided, the manganese source compound of this solubility and nickel source compound are stoichiometrically dissolved mixing in a solvent, form a nickel manganese mixed solution;
The carbonate solution with carbonate or bicarbonate radical is provided, this nickel manganese mixed solution and this carbonate solution are input to mix and blend in crystallization control reactor respectively simultaneously, and the pH value controlled in still is 8-10, the temperature controlled in still is 40 DEG C-60 DEG C, obtains product;
Separation of Solid and Liquid is carried out and drying to this product, obtains spherical powder;
By the heat treatment 4 hours-10 hours at 400 DEG C-600 DEG C of this spherical powder;
Spherical powder after this heat treatment is mixed with Li source compound, and calcines 8 hours-20 hours at 700 DEG C-900 DEG C, obtain spherical lithium nickel Mn oxide.
In above-mentioned steps, described manganese source compound and nickel source compound press the stoichiometric proportion mixing of manganese in Li, Ni, Mn oxide and nickel, and in the present embodiment, this Li, Ni, Mn oxide is LiNi
0.5mn
1.5o
4, the nickel in this manganese source compound and nickel source compound and the mol ratio of manganese are 1:3.
This manganese source compound can be MnSO
4h
2o, Mn (CH
3cOO)
2.
4h
2o and Mn (NO
3)
2.
4h
2one or more in O, described nickel source compound can be NiSO
4.
6h
2o, Ni (CH
3cOO)
2.
4h
2o and Ni (NO
3)
2.
6h
2one or more in O.In the present embodiment, this manganese source compound is MnSO
4h
2o, this nickel source compound NiSO
4.
6h
2o.Particularly, 50.7g MnSO
4h
2o and 26.3gNiSO
4.
6h
2o, is dissolved in 2L deionized water, is stirred well to whole dissolving, obtains nickel manganese mixed solution.In the present embodiment, this carbonate solution is 42.4gNa
2cO
3be dissolved in 2L deionized water, be stirred well to after all dissolving and formed.
Be input in the process of crystallization control reactor respectively by described carbonate solution and nickel manganese mixed solution, the charging flow velocity of described nickel manganese mixed solution is controlled is made as 2mL/min, and the charging flow velocity of described carbonate solution is controlled is made as 2.2mL/min.
The temperature of the temperature in described reactor has a certain impact for the reaction in reactor, also can affect the process of crystallization, and therefore, the temperature in still is unsuitable too low, and too low temperature is unfavorable for that reaction is carried out; Temperature is too high, is difficult to generate crystallization.In the present embodiment, the temperature in still can remain on 45 DEG C, and the pH value in still remains on about 8.In addition, mixing speed has a significant impact for the spheric granules pattern generated, and in the process be uniformly mixed, the rotating speed of stirring can remain on 1200rpm/min.In the present embodiment, the chemical formula of this spherical powder is Ni
0.5mn
1.5(CO
3)
2xH
2o.
Described by this spherical powder at 400 DEG C-600 DEG C in heat treated step, described heat treated temperature can be 420 DEG C.Spherical powder after heat treatment can be excessive with 1.5% Li source compound mix, this Li source compound can be Li
2cO
3, Li
2cO
3excessive is loss in order to make up lithium in calcination process.Described calcining step can carry out in Muffle furnace, and calcining heat can be 850 DEG C, and calcination time can be 16 hours.
Refer to Fig. 9, the spherical powder granular size before the heat treatment of being synthesized by crystallization control method is between 5 microns-30 microns.Refer to Figure 10, the spherical LiNi obtained after 420 DEG C and 850 DEG C of process
0.5mn
1.5o
4particle is still spherical morphology, but spheroid shrinks, spherical LiNi
0.5mn
1.5o
4particle diameter is 7 microns.
Further, carry out aluminum phosphate to this spherical lithium nickel Mn oxide coated, concrete grammar is: take appropriate Al (NO
3)
3.
9h
2o is dissolved in ethanol, is mixed with the alcoholic solution of 100g/L.Take appropriate (NH
4)
2hPO
4be dissolved in deionized water, be mixed with the aqueous solution of 100g/L.Take 1 gram of spherical lithium nickel Mn oxide, by Al (NO
3)
3alcoholic solution joins in spherical lithium nickel Mn oxide, stirs, more slowly drips (NH
4)
2hPO
4the aqueous solution, dropping limit, limit is stirred, until solution becomes muddy.Al (the NO added
3)
3with (NH
4)
2hPO
4mol ratio be 1:1.Slimy mixture is put into the drying in oven of 120 DEG C, then to put in Muffle furnace calcining and within 2 hours, obtain coated AlPO
4spherical lithium nickel Mn oxide.Wherein, the mass percent that phosphoric acid aluminium lamination accounts for aluminum phosphate-spherical lithium nickel manganese oxide composite material gross mass is 1%, and calcining heat selects 400 DEG C to obtain sample 1, and calcining heat selects 700 DEG C to obtain sample 2.
Further, with 700 DEG C for calcining heat, by changing the covering amount of phosphoric acid aluminium lamination, 2 kinds of different samples are prepared, wherein, the mass percent accounting for aluminum phosphate-spherical lithium nickel manganese oxide composite material gross mass at phosphoric acid aluminium lamination prepares sample 3 under being the condition of 2%, is prepare sample 4 under the condition of 3% with mass percent.
Refer to Figure 11, in Figure 11, curve (a) is not coated spherical LiNi
0.5mn
1.5o
4, curve (b) is the sample 1 of calcining heat 400 DEG C, and curve (c) is the sample 2 of calcining heat 700 DEG C.By the spherical LiNi with not coated aluminum phosphate
0.5mn
1.5o
4contrast, at the spherical LiNi of coated aluminum phosphate
0.5mn
1.5o
4xRD spectra in, position and the intensity of diffraction maximum do not change substantially, also do not have AlPO
4diffraction maximum occurs, coated AlPO is described
4layer is unbodied, AlPO
4with LiNi
0.5mn
1.5o
4also do not react.
Refer to Figure 12, sample 2 is analyzed by transmission electron microscope observing, can AlPO be seen
4coating layer is even, and thickness is at 10 ran.
By the aluminum phosphate in this aluminum phosphate-spherical lithium nickel manganese oxide composite material alternative embodiment 1-cobalt acid lithium composite material, be assembled into lithium ion battery under the same conditions as example 1, carry out charge-discharge performance test.
Contrast experiment 3
By the crystallization control method identical with embodiment 3, synthesizing spherical LiNi
0.5mn
1.5o
4, and by not coated spherical LiNi
0.5mn
1.5o
4as positive active material, be assembled into lithium ion battery at the same conditions as example 3, carry out charge-discharge performance test.
Refer to Figure 13, Figure 13 is the sample 3 of Application Example 3 respectively and not coated spherical LiNi
0.5mn
1.5o
4the lithium ion battery be assembled into, the first charge-discharge curve of constant current charge-discharge under 0.5C multiplying power.Adopt the charge and discharge platform of the lithium ion battery of sample 2 at about 4.7V, the spherical LiNi not coated with employing
0.5mn
1.5o
4lithium ion battery identical.The initial charge specific capacity of the lithium ion battery of sample 3 reaches 134.9 mAh/g, and specific discharge capacity reaches 126.2 mAh/g.With not coated spherical LiNi
0.5mn
1.5o
4lithium ion battery contrast, find that the coated specific capacity of positive active material that makes increases, this is due to coated AlPO
4layer plays the effect intercepting electrolyte effectively, and the HF that the decomposition reaction preventing under high pressure electrolyte from occurring generates corrodes positive electrode, causes portion capacity to lose.
Refer to sample 3 and not coated spherical LiNi that 14, Figure 14 is Application Example 3 respectively
0.5mn
1.5o
4lithium ion battery, the cycle performance curve of constant current charge-discharge under 1C, 3C and 5C multiplying power.As can be seen from Figure 14, not coated spherical LiNi
0.5mn
1.5o
4lithium ion battery along with the increase of charge-discharge magnification, special capacity fade obtains very fast, and under 5C multiplying power, specific discharge capacity is almost 0.The lithium ion battery first discharge specific capacity of sample 3 slightly declines than not coated battery, but along with the increase of cycle-index, specific capacity does not only decline, and slightly rises on the contrary, along with the increase of multiplying power, the decay of specific capacity is also obviously than adopting not coated spherical LiNi
0.5mn
1.5o
4battery much smaller.In addition, when adopting the lithium ion battery of sample 3 to discharge under 5C multiplying power, specific capacity declined before this, after improve significantly again, this is because AlPO along with cycle-index increase
4coating layer is at spherical LiNi
0.5mn
1.5o
4surface can increase the resistance of material, when making to start, and the embedding of ion and deviate to become difficulty, but along with the increase of cycle-index, after ion channel is set up, ion can successfully move again in the channel, so capacity also can increase thereupon.
Refer to Figure 15 and Figure 16, Figure 15 be the lithium ion battery of sample 2-4 under 1C multiplying power, voltage range is the first charge-discharge curve of 3.5V-4.9V.Figure 16 be the lithium ion battery of sample 2-4 under 1C multiplying power, voltage range is the cycle performance curve of 3.5V-4.9V.Can be seen by Figure 15, the charge/discharge capacity of sample 3 is higher.The specific capacity of the battery of sample 4 declines, and coated AlPO is described
4amount too high time, blocked up coating layer can cause Lithium-ion embeding and the obstacle deviate from, causes capacity lower.As seen from Figure 16, the cycle performance of the battery of sample 3 is best, and after 20 circulations, capacity also has 113.6 mAh/g.
In addition, those skilled in the art also can do other changes in spirit of the present invention, and certainly, these changes done according to the present invention's spirit, all should be included within the present invention's scope required for protection.
Claims (17)
1. a preparation method for lithium nickel manganese oxide composite material, it comprises:
Aluminum nitrate solution is provided;
Add in this aluminum nitrate solution by positive active material particle to be covered, form mixture, the volume ratio of the volume of this aluminum nitrate solution and this positive active material particle is 1:10 to 1:40, and the material of this positive active material particle is by chemical formula Li
xni
0.5+y-amn
1.5-y-bm
an
bo
4represent, wherein 0.1≤x≤1.1,0≤y<1.5,0≤a-y<0.5, and 0≤b+y<1.5, M and N are one or more in alkali metal, alkali earth metal, the 13rd race's element, the 14th race's element, transition element and rare earth element;
Phosphate solution is added this mixture to react, form phosphoric acid aluminium lamination at this positive active material particle surface; And
This surface of heat treatment has the positive active material particle of phosphoric acid aluminium lamination.
2. the preparation method of lithium nickel manganese oxide composite material as claimed in claim 1, it is characterized in that, described, positive active material particle to be covered is added in the step of this aluminum nitrate solution, control the addition of this positive active material further, make mixture be muddy.
3. the preparation method of lithium nickel manganese oxide composite material as claimed in claim 1, it is characterized in that, this aluminum nitrate solution comprises solvent and is dissolved in the aluminum nitrate of this solvent, and this solvent is ethanol.
4. the preparation method of lithium nickel manganese oxide composite material as claimed in claim 1, it is characterized in that, this phosphate solution comprises water and is dissolved in the phosphoric acid ammonia salt of water, and this phosphoric acid ammonia salt comprises the mixing of one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate and triammonium phosphate.
5. the preparation method of lithium nickel manganese oxide composite material as claimed in claim 1, it is characterized in that, this heat treatment temperature is 400 DEG C to 700 DEG C.
6. a lithium nickel manganese oxide composite material, prepared by the preparation method of lithium nickel manganese oxide composite material as claimed in claim 1, this lithium nickel manganese oxide composite material comprises positive active material particle, and the material of this positive active material particle is by chemical formula Li
xni
0.5+y-amn
1.5-y-bm
an
bo
4represent, wherein 0.1≤x≤1.1,0≤y<1.5,0≤a-y<0.5, and 0≤b+y<1.5, M and N are one or more in alkali metal, alkali earth metal, the 13rd race's element, the 14th race's element, transition element and rare earth element, it is characterized in that, comprise the phosphoric acid aluminium lamination being coated on this positive active material particle surface further, described aluminum phosphate layer thickness is even and continuous.
7. lithium nickel manganese oxide composite material as claimed in claim 6, it is characterized in that, the mass percent of described phosphoric acid aluminium lamination in this anode composite material particle is 0.1% to 3%.
8. lithium nickel manganese oxide composite material as claimed in claim 6, it is characterized in that, the mass percent of described phosphoric acid aluminium lamination in this anode composite material particle is 2%.
9. lithium nickel manganese oxide composite material as claimed in claim 6, it is characterized in that, the thickness of described phosphoric acid aluminium lamination is 5 nanometer to 20 nanometers.
10. lithium nickel manganese oxide composite material as claimed in claim 6, it is characterized in that, described phosphoric acid aluminium lamination is that in-situ preparation is at this positive active material particle surface.
11. lithium nickel manganese oxide composite material as claimed in claim 6, is characterized in that, the scope of described y is 0≤y<0.1.
12. lithium nickel manganese oxide composite material as claimed in claim 6, it is characterized in that, described M is selected from least one in Cr, Co, V, Ti, Al, Fe, Ga and Mg.
13. lithium nickel manganese oxide composite material as claimed in claim 6, is characterized in that, the chemical formula of the material of described positive active material particle is LiNi
0.5mn
1.5o
4.
14. lithium nickel manganese oxide composite material as claimed in claim 6, is characterized in that, the particle diameter of described positive active material particle is 100 nanometers to 100 micron.
15. lithium nickel manganese oxide composite material as claimed in claim 14, is characterized in that, the particle diameter of described positive active material particle is 1 micron to 20 microns.
16. 1 kinds of lithium ion batteries, it comprises positive pole, it is characterized in that, this positive pole comprises lithium nickel manganese oxide composite material as claimed in claim 6.
17. lithium ion batteries as claimed in claim 16, it is characterized in that, be 5V at charge cutoff voltage, discharge cut-off voltage be the scope of 3V carry out constant current charge-discharge circulate to have after 50 times more than 95% capability retention.
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| CN102447106B (en) * | 2010-10-15 | 2014-03-26 | 清华大学 | Spinel lithium manganate composite material and preparation method thereof as well as lithium ion battery |
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| WO2019103461A2 (en) | 2017-11-21 | 2019-05-31 | 주식회사 엘지화학 | Cathode active material precursor, manufacturing method therefor, and cathode active material, cathode and secondary battery manufactured by using same |
| KR102313092B1 (en) * | 2018-04-04 | 2021-10-18 | 주식회사 엘지화학 | Method of manufacturing positive electrode active material for lithium secondary battery, positive electrode active material for lithium secondary, positive electrode for lithium secondary and lithium secondary comprising the same |
| CN111180822B (en) * | 2020-02-05 | 2021-06-22 | 中国科学院化学研究所 | Recycling method of nickel-cobalt-manganese waste ternary lithium battery positive electrode material |
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Non-Patent Citations (1)
| Title |
|---|
| Improved electrochemical performance of AlPO4-coated LiMn1.5Ni0.5O4 electrode for lithium-ion batteries;Jin Yi Shi等;《Journal of Power Sources》;20101001;第195卷(第19期);6860-6866 * |
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