CN100385712C - Multicomponent metal oxide, lithium ion battery anode material and its preparing method - Google Patents
Multicomponent metal oxide, lithium ion battery anode material and its preparing method Download PDFInfo
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- CN100385712C CN100385712C CNB2004100409363A CN200410040936A CN100385712C CN 100385712 C CN100385712 C CN 100385712C CN B2004100409363 A CNB2004100409363 A CN B2004100409363A CN 200410040936 A CN200410040936 A CN 200410040936A CN 100385712 C CN100385712 C CN 100385712C
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- lithium
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 30
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- 239000010405 anode material Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 67
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000010941 cobalt Substances 0.000 claims abstract description 27
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 27
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011777 magnesium Substances 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 150000001868 cobalt Chemical class 0.000 claims abstract description 15
- 150000002815 nickel Chemical class 0.000 claims abstract description 15
- 159000000013 aluminium salts Chemical class 0.000 claims abstract description 9
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 9
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- 238000002360 preparation method Methods 0.000 claims description 38
- 239000007788 liquid Substances 0.000 claims description 36
- 229910021529 ammonia Inorganic materials 0.000 claims description 33
- 150000003863 ammonium salts Chemical class 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 5
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 abstract 4
- 238000010668 complexation reaction Methods 0.000 abstract 2
- 229910018404 Al2 O3 Inorganic materials 0.000 abstract 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 229910013179 LiNixCo1-xO2 Inorganic materials 0.000 abstract 1
- 229910013171 LiNixCo1−xO2 Inorganic materials 0.000 abstract 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 abstract 1
- 239000007921 spray Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 23
- 229910013716 LiNi Inorganic materials 0.000 description 22
- 239000002245 particle Substances 0.000 description 13
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 12
- 235000011130 ammonium sulphate Nutrition 0.000 description 12
- 229910016970 Ni0.85Co0.15(OH)2 Inorganic materials 0.000 description 9
- 238000000975 co-precipitation Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 229910015724 LiNi0.85Co0.15O2 Inorganic materials 0.000 description 6
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 4
- MXEHMOBFYMIGAE-UHFFFAOYSA-L cobalt(2+);nickel;dihydroxide Chemical compound [OH-].[OH-].[Co+2].[Ni] MXEHMOBFYMIGAE-UHFFFAOYSA-L 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910011324 LiNi0.6Co0.4O2 Inorganic materials 0.000 description 2
- 229910013292 LiNiO Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000001174 ascending effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PLMWDYFOEVVFHN-UHFFFAOYSA-N azane;5-[1-(3-carboxy-5-chloro-4-hydroxyphenyl)undecyl]-3-chloro-2-hydroxybenzoic acid Chemical compound N.C=1C(Cl)=C(O)C(C(O)=O)=CC=1C(CCCCCCCCCC)C1=CC(Cl)=C(O)C(C(O)=O)=C1 PLMWDYFOEVVFHN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 208000021760 high fever Diseases 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Images
Classifications
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- 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
Abstract
The present invention relates to a method for preparing spherical nickelous hydroxide doped with cobalt. Divalent nickel salt and cobalt salt are firstly mixed with ammonia water and ammonia salt to form complexation solution; the formed complexation solution and alkali liquor flow and are added into a reaction container together, spherical nickelous hydroxide sedimentation doped with the cobalt is generated, and foreign ions are washed and removed. The present invention also relates to a multi-element metal oxide. The LiNixCo1-xO2 (0<x<1) surface is doped and coated with one layer of metal oxides which are preferable to be Al2 O3 mixed oxides or MgO mixed oxides or Al and Mg mixed oxides. A method for preparing the multi-element metal oxide is that the manufactured spherical nickelous hydroxide doped with the cobalt is added with lithium hydroxide and aluminium salt or magnesium salt or the mixed solution of the lithium hydroxide, the aluminium salt and the magnesium salt, spray and dryness are carried out after uniform mixing, and the spherical nickelous hydroxide doped with the cobalt is sintered at high temperature. The multi-element metal oxide is particularly suitable for being used as anode materials of a lithium ion battery.
Description
Technical field
The present invention relates to multi-element metal oxide and preparation method thereof, relate in particular to LiNi
xCo
1-xO
2Modification, be particularly suitable for the positive electrode as lithium ion battery.
Background technology
LiNi
xCo
1-xO
2Not only possessed LiCoO
2Characteristic (easily synthetic, stable performance), more have LiNiO concurrently
2Height ratio capacity, advantage cheaply.And in charge and discharge process LiNi
xCo
1-xO
2Pure LiNiO does not take place
2Three phase transformations that material experienced, thereby have better cycle performance.Simultaneously, LiNi
xCo
1-xO
2Irreversible capacity can provide the lithium source for the formation that negative pole forms the SEI film, thereby reduce anodal overhead provision.At present, LiNi
xCo
1-xO
2Reversible specific capacity can reach 180mAh/g.
LiNi
xCo
1-xO
2Modification mainly take off the embedding stability of structure, suppress or slow down phase transformation and set about from raising, main method has mixes and coats.Other transition metal ions is to LiNi
xCo
1-xO
2Doping again, further improved the stability of material.LiNi after surface doping coats
xCo
1-xO
2First discharge specific capacity descends to some extent, but because LiNi has been avoided in the existence of coating layer
xCo
1-xO
2Contact with the direct of electrolyte, suppressed pernicious interaction, further improved the cycle performance of material.
Coprecipitation is preparation LiNi
xCo
1-xO
2And a kind of easy, the practical method of mixing and coating on its surface.In coprecipitation, the preparation that sphere is mixed the cobalt hickelous nydroxide is preparation high-performance LiNi
xCo
1-xO
2Key link.
Publication number is that the Chinese patent of CN1216289A discloses the application for a patent for invention (documents) that a kind of name is called " lithium composite xoide, its method for making and with its lithium battery as active material of positive electrode ", it prepares spherical method of mixing the cobalt hickelous nydroxide (is the step a in the claim 1: will add in the mixed aqueous solution that contains cobalt salt and nickel salt co-precipitation Ni-Co complex hydroxide as the ammonia spirit of complexing agent with as a kind of aqueous slkali of pH value conditioning agent; ) there is following deficiency: 1, because the pH value is difficult to control, the sphere that generates is mixed cobalt hickelous nydroxide granular size inequality: because ammoniacal liquor and aqueous slkali are to add gradually in the mixed aqueous solution of cobalt salt and nickel salt, thereby the pH value in the mixed solution is ascending, the pH value is minimum when promptly beginning, and adds pH value maximum when finishing.Because spherical settling velocity of mixing the cobalt hickelous nydroxide is directly proportional with the pH value, the deposit seed size that sphere is mixed the cobalt hickelous nydroxide is inversely proportional to settling velocity, thereby pH value hour settling velocity is slow, it is bigger that the sphere that generates is mixed cobalt hickelous nydroxide particle, the corresponding increase of settling velocity when the pH value increases, the sphere of generation is mixed corresponding the diminishing of cobalt hickelous nydroxide particle, in the whole precipitation process, it is descending that the sphere that generates is mixed cobalt hickelous nydroxide particle, thereby size is inhomogeneous.2, because ammoniacal liquor and aqueous slkali add the mixed solution of nickel salt and cobalt salt simultaneously, the nickel cobalt also is not able to do in time to form before the complex solution directly with ammoniacal liquor and aqueous slkali reaction generation precipitates, ammoniacal liquor does not just play the effect of crystallization control speed so, crystal grain be difficult to grow up form spherical.3, this clearance-type production owned by France, efficient is low, is unfavorable for industrialization production.4, this invention lithium composite xoide (Li
aNi
1-xCo
xO
2, a=0.97-1.05 in the formula, first discharge specific capacity x=0.1-0.3) has only 160mAh/g.
At present, with the button cell experiment, general by the LiNi after coating at surface doping
xCo
1-xO
2First discharge specific capacity＞170mAh/g, the 100 cycle specific capacities that circulate remain on about 100mAh/g.
Summary of the invention
One of purpose of the present invention is to provide a kind of uniform particles that can make sphere mix the cobalt hickelous nydroxide, mixes the preparation method that cobalt sphere even, that help industrialization production is mixed the cobalt hickelous nydroxide.
Another object of the present invention is to provide a kind of multi-element metal oxide and preparation method thereof with high conduction performance and cycle performance.Utilize spherical hickelous nydroxide to prepare LiNi
xCo
1-xO
2, and at LiNi
xCo
1-xO
2Carry out modification, the coating of mixing on its surface improves LiNi
xCo
1-xO
2Electric conductivity and cycle performance.
Another purpose of the present invention is to provide a kind of anode material for lithium-ion batteries and a kind of lithium rechargeable battery its preparation method with high conduction performance and cycle performance.
The technical scheme that realizes above-mentioned purpose is:
A kind of sphere is mixed the preparation method of cobalt hickelous nydroxide, comprises the steps:
1) the formation complex solution mixes with nickel salt, the cobalt salt of divalence in elder generation with ammoniacal liquor, ammonium salt;
2) add in the reaction vessel with the formed complex solution of step 1) and alkali lye and stream again, stir the generation sphere and mix cobalt hickelous nydroxide precipitation, foreign ion is removed in washing.
A kind of preparation method of multi-element metal oxide comprises the steps:
1) the formation complex solution mixes with nickel salt, the cobalt salt of divalence in elder generation with ammoniacal liquor, ammonium salt;
2) add in the reaction vessel with the formed complex solution of step 1) and alkali lye and stream again, stir the generation sphere and mix cobalt hickelous nydroxide precipitation, foreign ion is removed in washing;
3) add lithium hydroxide and slaine mixed solution in the precipitation after washing, spray-dried behind the mixing, make finished product through high temperature sintering again, described slaine is selected from aluminium salt, magnesium salts or both mixing, and the temperature of described high temperature sintering is 700～800 ℃.
Also be added with end liquid in the described reaction vessel, end liquid is the mixing cushioning liquid of ammoniacal liquor and ammonium salt, ammonia concn in the end liquid is lower than the ammonia concn described in the step 1), and end liquid consumption can just stretch into the end liquid that is arranged in container bottom with the lower end of stirring arm and end liquid stirred and be as the criterion.
Preferably: described ammonia concn is 0.1～1mol/L, and ammonium salt concentration is 0.02～0.25mol/L, and the mol ratio of ammoniacal liquor and ammonium salt is 5: 1～4: 1, ammonium salt employing and nickel salt or the identical salt of cobalt salt acid group.Ammonia concn in the end liquid equals half of the ammonia concn described in the step 1).
Nickel salt and cobalt salt are sulfate, nitrate, chlorate or acetate, alkali is NaOH or KOH, the mol ratio of salt and alkali is 1: 2.1～1: 2.4, aluminium salt, magnesium salts are nitrate or acetate, and the mol ratio of Ni, Co, Al sum or Ni, Co, Mg sum or Ni, Co, Al, Mg sum and monohydrate lithium hydroxide is 1: 1.02～1: 1.07; Mixing speed is 100～600r/min; The spray drying temperature is 150～200 ℃; The high temperature sintering temperature is 700～800 ℃, and sintering time is 12～24 hours.
Above-mentioned multi-element metal oxide is suitable for as anode material for lithium-ion batteries.
A kind of multi-element metal oxide is at LiNi
xCo
1-x0
2Surface doping coated one deck Al
20
3Or the mixed oxide of MgO or Al, Mg, wherein, x=0.6～0.85, the mol ratio of Ni, Co summation and Al or Mg or Al, Mg summation (Al, Mg can be any ratios) is 0.9: 0.1～0.95: 0.05.
A kind of anode material for lithium-ion batteries is at LiNi
xCo
1-x0
2Surface doping coated one deck Al
2O
3Or the mixed oxide of MgO or Al, Mg, wherein, x=0.6～0.85, the mol ratio of Ni, Co summation and Al or Mg or Al, Mg summation (Al, Mg can be any ratios) is 0.9: 0.1～0.95: 0.05.
A kind of lithium rechargeable battery comprises a kind of positive pole that contains lithia as active material, and wherein Zheng Ji lithia is above-mentioned multi-element metal oxide.
Adopt technique scheme, in conjunction with the following embodiment that will describe in detail, beneficial technical effects of the present invention is: 1, when the preparation sphere is mixed the cobalt hickelous nydroxide, because before co-precipitation, elder generation is with the nickel salt of divalence, cobalt salt and ammoniacal liquor, ammonium salt mix to form complex solution (ammonium salt and the ammonia cushioning liquid about can shape pH=7, precipitation can not appear in complex solution, main purpose is that cobalt is not precipitated), again complex solution is added in the reaction vessel with alkali lye and stream and react, generate sphere and mix cobalt hickelous nydroxide precipitation, effectively avoided the direct adding of alkali lye to cause particle to be difficult to grow up and formed spherical problem; 2, because to be complex solution with alkali lye and stream add generates sphere in the reaction vessel and mix the cobalt hickelous nydroxide and precipitate, as long as it is constant that inflow velocity keeps, pH value in the reaction vessel can keep constant, the ascending problem of pH value can not appear, thereby, adopt the inventive method to guarantee to generate in the reaction vessel spherical speed and even particle size of mixing the cobalt hickelous nydroxide.3, owing to liquid at the bottom of the mixing cushioning liquid that in reaction vessel, is added with ammoniacal liquor and ammonium salt, guaranteed when reinforced at the beginning, the complex solution of adding and alkali lye are stirred, and the existence of bottom cushioning liquid can to guarantee to react the fluctuation of pH value when beginning very little.4, mix the cobalt hickelous nydroxide owing to adopt above-mentioned crystallization control legal system to be equipped with sphere, preparation technology is simple, process is controlled easily, does not need that reaction vessel is done " emptying " and handles, and can produce production efficiency height, suitable for mass production continuously.5, because at LiNi
xCo
1-xO
2Surface doping coated the layer of metal oxide, particularly preferred Al
2O
3Or the mixed oxide of MgO or Al, Mg, reduced inner Ni and contacted with the direct of electrolyte, effectively suppressed side reaction, improved LiNi
xCo
1-xO
2With the compatibility of electrolyte, improved the cycle performance of material greatly.Simultaneously, the Al, the Mg that have part in sintering process enter inner formation of crystal grain and mix, and have improved the conductivity of material, help giving full play to of capacity, can suppress changes of crystal in the charge and discharge process simultaneously, have improved the stability of material.6, by in the wet-mixed that adds lithium hydroxide and aluminium salt or magnesium salts or three of mixing in the cobalt spherical hickelous nydroxide for preparing, spray drying behind mixing, high temperature sintering not only coats one deck Al on the surface
2O
3Or the mixed oxide of MgO or Al, Mg, and can reach the even mixing of molecular level, high fever promptly can not contained the LiNi of dephasign
1-x-yCo
xAl
yO
27, show according to Fig. 1-5 data: the multi-element metal oxide (LiNi that adopts the inventive method preparation
1-x-yCo
xAl
yO
2) particle size distribution be 6～10 μ m, the first charge-discharge specific capacity can reach 170mAh/g, first charge-discharge efficiency is nearly 80%, tap density is 2.4g/cm
3, both kept higher specific capacity, higher tap density is arranged again, the surface coats LiNi
1-x-yCo
xAl
yO
2Cycle performance is good.With the button cell experiment, 100 cycles that circulate still have the specific capacity of 120mAh/g.High voltage withstanding, charging can be to 4.5V, and security performance is good.In sum, integrated performance indexs such as its high conduction performance of multi-element metal oxide of the present invention's preparation and cycle performance obviously are better than documents and other prior art, can be used as lithium rechargeable battery fully.
Description of drawings
Fig. 1 is the grain size analysis figure of a kind of multi-element metal oxide (hereinafter to be referred as product).
Fig. 2 adopts the definite product particle thing phase XRD spectra of X-ray diffractometer (XRD).
Fig. 3 is the particle SEM photo that utilizes the product that ESEM (SEM) photographs.
Fig. 4 is a product first charge-discharge curve.
Fig. 5 is a product cycle performance curve.
Before Fig. 6 coats and coating back cycle performance is to curve.
Embodiment
Embodiment 1: a kind of multi-element metal oxide is at LiNi
0.85Co
0.15O
2Surface doping coat one deck Al
2O
3
The preparation method of above-mentioned multi-element metal oxide:, add in the 40L reactor Ni with NaOH and stream with the complexing alkali lye of nickelous sulfate, cobaltous sulfate and ammoniacal liquor, ammonium sulfate
2+And Co
2+Mol ratio be 0.85: 0.15, total salinity is 1mol/L, ammonia concentration is 1mol/L, ammonium sulfate concentrations is 0.22mol/L, and NaOH concentration is 2.3mol/L, and end liquid is the mixed solution of ammonia and ammonium sulfate, ammonia concentration is 0.5mol/L, ammonium salt concentration is 0.11mol/L, and end liquid consumption stirs just to mix with stirring arm and is as the criterion, control charging rate 1L/h, 50 ℃ of reaction temperatures, pH value 11.5, mixing speed 500r/min, co-precipitation obtains graminaceous sphere and mixes cobalt hydroxide nickel
0.85Co
0.15(OH)
2, ageing 2h removes SO 5～7 times with the distilled water washing
4 2-Preparation LiOH and Al (NO
3)
3Mixed solution, Ni
0.85Co
0.15(OH)
2With the mol ratio of LiOH be 1: 1.05, the mol ratio of nickel cobalt and aluminium is 0.95: 0.05), with Ni
0.85Co
0.15(OH)
2Add LiOH and Al (NO
3)
3Mixed solution, stir the back obtain evengranular presoma in 200 ℃ of spray dryings.Place resistance furnace with 5 ℃ heating rate to 700 ℃ in forerunner's alms bowl crucible of packing into, constant temperature 24h treats that temperature reduces to below 200 ℃, takes out crucible, and ball mill grinding can obtain the anode material for lithium-ion batteries of high power capacity, high voltage withstanding, good cycle.
Product with present embodiment preparation carries out structure and performance characterization by following means: adopt thing that X-ray diffractometer (XRD) determines particle mutually, utilize the shape and size of ESEM (SEM) Direct observation product, the chemical property of product detects with button cell.
According to shown in Figure 1, average grain diameter is 8 μ m, not only coats one deck Al on the surface
2O
3, and reach the even mixing of molecular level.
According to the determined product particle thing of Fig. 2 phase XRD spectra, there are not assorted peak in position and number from diffraction maximum, showing that the coating of mixing does not bring other dephasigns, this feature to show that product has regular layer structure yet.
According to the particle SEM photo of Fig. 3 product, the particle subglobular of product as can be seen, sphere helps giving full play to of capacity.
According to Fig. 4 first charge-discharge curve as can be seen, be product first charge-discharge curve.High voltage withstanding, charging can be to 4.5V, and security performance is good.Initial charge specific capacity 210mAh/g, specific discharge capacity 170mAh/g, efficiency for charge-discharge 81%.
According to Fig. 5 product cycle performance curve, from first to second circulation volume attenuation ratio is bigger, but this also provides sufficient lithium source for negative terminal surface forms the SEI film.Capability retention is all more than 99% in the circulation afterwards, and 100 specific capacities that circulate still remain on more than the 120mAh/g.
This shows that the present embodiment multi-element metal oxide is a kind of anode material for lithium-ion batteries with high conduction performance and cycle performance.
Embodiment 2, a kind of multi-element metal oxide are at LiNi
0.6Co
0.4O
2Surface doping coat one deck Al
2O
3
The preparation method of above-mentioned multi-element metal oxide: present embodiment and embodiment one difference are: x=0.6, multi-element metal oxide LiNi
0.6Co
0.4O
2(0＜x＜1), i.e. Ni
2+And Co
2+Mol ratio be 0.6: 0.4, total salinity is 1mol/L, the mol ratio of nickel cobalt and aluminium is 0.9: 0.1, other condition and preparation method are with embodiment 1.The product average grain diameter that makes is 8 μ m, initial charge specific capacity 220mAh/g, and specific discharge capacity 180mAh/g, first charge-discharge efficiency are 82%, tap density 2.4g/cm
3With the button cell experiment, the 100 cycle specific capacities that circulate remain on 110mAh/g.
Embodiment 3, present embodiment and embodiment one difference are: ammonia concentration 1mol/L, and alkali concn 2mol/L, pH value 11.5, other condition and preparation method are with embodiment 1.The product average grain diameter that makes is 9 μ m, initial charge specific capacity 200mAh/g, and specific discharge capacity 160mAh/g, first charge-discharge efficiency are 80%, tap density 2.5g/cm
3With the button cell experiment, the 100 cycle specific capacities that circulate remain on 110mAh/g.
Embodiment 5, present embodiment and embodiment one difference are: 70 ℃ of coprecipitation reaction temperature, and mixing speed 120r/min, other condition and preparation method are with embodiment 1.The product average grain diameter that makes is 7 μ m, initial charge specific capacity 220mAh/g, and specific discharge capacity 170mAh/g, first charge-discharge efficiency are 77%, tap density 2.3g/cm
3With the button cell experiment, the 100 cycle specific capacities that circulate remain on 120mAh/g.
Embodiment 6, present embodiment and embodiment one difference are: Ni
0.85Co
0.15(OH)
2With the mol ratio of LiOH be 1: 1.07,800 ℃ of constant temperature sintering 12h.The product average grain diameter that makes is 8 μ m, initial charge specific capacity 210mAh/g, and specific discharge capacity 160mAh/g, first charge-discharge efficiency are 76%, tap density 2.4g/cm
3With the button cell experiment, the 100 cycle specific capacities that circulate remain on 110mAh/g.
Embodiment 7, a kind of multi-element metal oxide are at LiNi
0.85Co
0.15O
2Surface doping coat one deck MgO.
The preparation method of above-mentioned multi-element metal oxide:, add in the 40L reactor Ni with NaOH and stream with the complexing alkali lye of nickelous sulfate, cobaltous sulfate and ammoniacal liquor, ammonium sulfate
2+And Co
2+Mol ratio be 0.85: 0.15, total salinity is 1mol/L, ammonia concentration is 1mol/L, ammonium sulfate concentrations is 0.22mol/L, and NaOH concentration is 2.3mol/L, and end liquid is the mixed solution of ammonia and ammonium sulfate, ammonia concentration is 0.5mol/L, ammonium salt concentration is 0.11mol/L, and end liquid consumption stirs just to mix with stirring arm and is as the criterion, control charging rate 1L/h, 50 ℃ of reaction temperatures, pH value 11.5, mixing speed 500r/min, co-precipitation obtains graminaceous sphere and mixes cobalt hydroxide nickel
0.85Co
0.15(OH)
2, ageing 2h removes SO 5～7 times with the distilled water washing
4 2-Preparation LiOH and Mg (NO
3)
2Mixed solution (Ni
0.85Co
0.15(OH)
2With the mol ratio of LiOH be 1: 1.05, the mol ratio of nickel cobalt and magnesium is 0.95: 0.05), with Ni
0.85Co
0.15(OH)
2Add LiOH and Mg (NO
3)
2Mixed solution, stir the back obtain evengranular presoma in 200 ℃ of spray dryings.Place resistance furnace with 5 ℃ heating rate to 700 ℃ in forerunner's alms bowl crucible of packing into, constant temperature 24h, treat that temperature reduces to below 200 ℃, take out crucible, ball mill grinding, the product average grain diameter that obtains is 8 μ m, surface doping has coated one deck MgO, first discharge specific capacity 170mAh/g, the 100 cycle specific capacities that circulate are 110mAh/g.
Embodiment 8, a kind of multi-element metal oxide are at LiNi
0.85Co
0.15O
2Surface doping coat one deck Al
2O
3And MgO.
The preparation method of above-mentioned multi-element metal oxide:, add in the 40L reactor Ni with NaOH and stream with the complexing alkali lye of nickelous sulfate, cobaltous sulfate and ammoniacal liquor, ammonium sulfate
2+And Co
2+Mol ratio be 0.85: 0.15, total salinity is 1mol/L, ammonia concentration is 1mol/L, ammonium sulfate concentrations is 0.22mol/L, and NaOH concentration is 2.3mol/L, and end liquid is the mixed solution of ammonia and ammonium sulfate, ammonia concentration is 0.5mol/L, ammonium salt concentration is 0.11mol/L, and end liquid consumption stirs just to mix with stirring arm and is as the criterion, control charging rate 1L/h, 50 ℃ of reaction temperatures, pH value 11.5, mixing speed 500r/min, co-precipitation obtains graminaceous sphere and mixes cobalt hydroxide nickel
0.85Co
0.15(OH)
2, ageing 2h removes SO 5～7 times with the distilled water washing
4 2-Preparation LiOH and Al (NO
3)
3, Mg (NO
3)
2Mixed solution (Ni
0.85Co
0.15(OH)
2With the mol ratio of LiOH be 1: 1.05), the mol ratio of aluminium and magnesium is 2: 1, the mol ratio of nickel cobalt and magnalium is 0.95: 0.05), with Ni
0.85Co
0.15(OH)
2Add LiOH and and Al (NO
3)
3, Mg (NO
3)
2Mixed solution, stir the back obtain evengranular presoma in 200 ℃ of spray dryings.Place resistance furnace with 5 ℃ heating rate to 700 ℃ in forerunner's alms bowl crucible of packing into, constant temperature 24h, treat that temperature reduces to below 200 ℃, take out crucible, ball mill grinding, the product average grain diameter that obtains are about 9 μ m, and surface doping has coated the mixed oxide of one deck Al and Mg, first discharge specific capacity 170mAh/g, the 100 cycle specific capacities that circulate are 120mAh/g.
Embodiment 9: a kind of multi-element metal oxide is at LiNi
0.85Co
0.15O
2The surface coat one deck Al
2O
3
The preparation method of above-mentioned multi-element metal oxide:, add in the 40L reactor Ni with NaOH and stream with the complexing alkali lye of nickelous sulfate, cobaltous sulfate and ammoniacal liquor, ammonium sulfate
2+And Co
2+Mol ratio be 0.85: 0.15, total salinity is 1mol/L, ammonia concentration is 1mol/L, ammonium sulfate concentrations is 0.22mol/L, and NaOH concentration is 2.3mol/L, and end liquid is the mixed solution of ammonia and ammonium sulfate, ammonia concentration is 0.5mol/L, ammonium salt concentration is 0.11mol/L, and end liquid consumption stirs just to mix with stirring arm and is as the criterion, control charging rate 1L/h, 50 ℃ of reaction temperatures, pH value 11.5, mixing speed 500r/min, co-precipitation obtains graminaceous sphere and mixes cobalt hydroxide nickel
0.85Co
0.15(OH)
2, ageing 2h removes SO 5～7 times with the distilled water washing
4 2-, 60 ℃ of oven dry, ball mill grinding.Preparation LiOH solution, Ni
0.85Co
0.15(OH)
2With the mol ratio of LiOH be 1: 1.05, with Ni
0.85Co
0.15(OH)
2Add LiOH solution, the back that stirs obtains single-size in 200 ℃ of spray dryings, and the crucible of packing into places resistance furnace with 5 ℃ heating rate to 700 ℃, and constant temperature 24h treats that temperature reduces to below 200 ℃, takes out crucible, and ball mill grinding can obtain LiNi
0.85Co
0.15O
2Dispose Al (NO then
3)
3Solution, the mol ratio of nickel cobalt and aluminium is 0.95: 0.05, and the back that stirs obtains single-size in 200 ℃ of spray dryings, and 500 ℃, constant temperature 10h can obtain the anode material for lithium-ion batteries of high power capacity, high voltage withstanding, good cycle.
According to Fig. 6 product cycle performance curve, LiNi
0.85Co
0.15O
2Before cycle performance after the coating obviously was better than coating, 100 specific capacities of circulation decayed to below the 100mAh/g before coating, and still remain on more than the 120mAh/g and coat back 100 specific capacities of circulation.
Claims (10)
1. the preparation method of a multi-element metal oxide comprises the steps:
1) the formation complex solution mixes with nickel salt, the cobalt salt of divalence in elder generation with ammoniacal liquor, ammonium salt;
2) add in the reaction vessel with the formed complex solution of step 1) and alkali lye and stream again, stir the generation sphere and mix cobalt hickelous nydroxide precipitation, foreign ion is removed in washing;
3) add lithium hydroxide and slaine mixed solution in the precipitation after washing, spray-dried behind the mixing, make finished product through high temperature sintering again, described slaine is selected from aluminium salt, magnesium salts or both mixing, and the temperature of described high temperature sintering is 700～800 ℃.
2. preparation method according to claim 1, described ammonia concn is 0.1～1mol/L, and ammonium salt concentration is 0.02～0.25mol/L, and the mol ratio of ammonia and ammonium salt is 5: 1～4: 1 in the ammoniacal liquor, ammonium salt employing and nickel salt or the identical salt of cobalt salt acid group.
3. preparation method according to claim 2, also be added with end liquid in the described reaction vessel, end liquid is the mixing cushioning liquid of ammoniacal liquor and ammonium salt, ammonia concn in the end liquid is lower than the ammonia concn described in the step 1), and end liquid consumption can just stretch into the end liquid that is arranged in container bottom with the lower end of paddle and end liquid stirred and be as the criterion.
4. preparation method according to claim 3, the ammonia concn in the end liquid equals half of the ammonia concn described in the step 1).
5. according to the preparation method of the described multi-element metal oxide of claim 1, it is characterized in that: described nickel salt and cobalt salt are sulfate, nitrate, chlorate or acetate, alkali is NaOH or KOH, the mol ratio of salt and alkali is 1: 2.1～1: 2.4, aluminium salt, magnesium salts are nitrate or acetate, and the mol ratio of Ni, Co, Al sum or Ni, Co, Mg sum or Ni, Co, Al, Mg sum and monohydrate lithium hydroxide is 1: 1.02～1: 1.07; Mixing speed is 100～600r/min, and the spray drying temperature is 150～200 ℃; The high temperature sintering time is 12～24 hours.
6. the preparation method of an anode material for lithium-ion batteries comprises the steps:
1) the formation complex solution mixes with nickel salt, the cobalt salt of divalence in elder generation with ammoniacal liquor, ammonium salt;
2) add in the reaction vessel with the formed complex solution of step 1) and alkali lye and stream again, stir the generation sphere and mix cobalt hickelous nydroxide precipitation, foreign ion is removed in washing;
3) add lithium hydroxide and slaine mixed solution in the precipitation after washing, spray-dried behind the mixing, make finished product through high temperature sintering again, described slaine is selected from aluminium salt, magnesium salts or both mixing, and the temperature of described high temperature sintering is 700～800 ℃.
7. according to the preparation method of the described anode material for lithium-ion batteries of claim 6, described ammonia concn is 0.1～1mol/L, ammonium salt concentration is 0.02～0.25mol/L, and the mol ratio of ammonia and ammonium salt is 5: 1～4: 1 in the ammoniacal liquor, ammonium salt employing and nickel salt or the identical salt of cobalt salt acid group.
8. according to the preparation method of the described anode material for lithium-ion batteries of claim 7, be added with end liquid in the reaction vessel, end liquid is the cushioning liquid of ammoniacal liquor and ammonium salt, ammonia concn in the end liquid is lower than the ammonia concn described in the step 1), and end liquid consumption can just stretch into the end liquid that is arranged in container bottom with the lower end of paddle and end liquid stirred and be as the criterion.
9. the preparation method of described anode material for lithium-ion batteries according to Claim 8, the ammonia concn in the end liquid equals half of the ammonia concn described in the step 1).
10. according to the preparation method of any described anode material for lithium-ion batteries of claim 6-9, it is characterized in that: described nickel salt and cobalt salt are sulfate, nitrate, chlorate or acetate, alkali is NaOH or KOH, the mol ratio of salt and alkali is 1: 2.1～1: 2.4, aluminium salt and magnesium salts are nitrate or acetate, and the mol ratio of Ni, Co, Al sum or Ni, Co, Mg sum or Ni, Co, Al, Mg sum and monohydrate lithium hydroxide is 1: 1.02～1: 1.07; Mixing speed is 100～600r/min, and the spray drying temperature is 150～200 ℃; The high temperature sintering time is 12～24 hours.
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| HK06110841A HK1088993A1 (en) | 2004-10-26 | 2006-09-29 | Multi-metal oxides, positive electrode materials for lithium-ion battery and preparation method thereof |
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| CN100511777C (en) * | 2007-07-13 | 2009-07-08 | 张家港市国泰华荣化工新材料有限公司 | A making method of cathode material for lithium ion battery |
| CN101834291B (en) * | 2010-04-09 | 2012-01-11 | 中南大学 | Preparation method of submicron level LiniO.5MnO.5O2 cathode material |
| CN103178262B (en) * | 2011-12-23 | 2016-02-03 | 西安物华新能源科技有限公司 | A kind of preparation method of aluminum-doped nickel lithium carbonate for lithium positive electrode |
| CN102969496A (en) * | 2012-11-20 | 2013-03-13 | 深圳市天骄科技开发有限公司 | Preparation method for saline solution doped with oxide of anode material of lithium ion battery |
| CN103050675A (en) * | 2012-12-21 | 2013-04-17 | 河南红日锂能源科技有限公司 | Aluminum-coated nickel cobalt magnesium lithium cathode material and preparation method thereof |
| CN104752712A (en) * | 2013-12-30 | 2015-07-01 | 北京当升材料科技股份有限公司 | A preparing method of a nickel cobalt lithium aluminate cathode material |
| CN104393277B (en) * | 2014-10-20 | 2017-05-17 | 上海空间电源研究所 | Ternary material coated with metal oxide on surface and used for lithium ion battery, and preparation method of ternary material |
| CN111807425A (en) * | 2020-08-07 | 2020-10-23 | 中国科学院长春应用化学研究所 | Method for preparing high-performance ternary positive electrode material of lithium ion battery under low ammonia concentration |
| CN112151797B (en) * | 2020-08-21 | 2021-09-14 | 湖南长远锂科股份有限公司 | Lithium-rich manganese-based positive electrode material coated by multi-metal composite oxide and preparation method thereof |
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| CN1193605A (en) * | 1997-03-14 | 1998-09-23 | 清华大学 | Preparation of high density and activity spherical nickle hydroxide |
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