CN1868895A - Synthesis method of ball-shaped mixed with/nickelnous hydroxide and multielement metal oxide and battery - Google Patents
Synthesis method of ball-shaped mixed with/nickelnous hydroxide and multielement metal oxide and battery Download PDFInfo
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- CN1868895A CN1868895A CNA2005100210138A CN200510021013A CN1868895A CN 1868895 A CN1868895 A CN 1868895A CN A2005100210138 A CNA2005100210138 A CN A2005100210138A CN 200510021013 A CN200510021013 A CN 200510021013A CN 1868895 A CN1868895 A CN 1868895A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 32
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 20
- 150000004706 metal oxides Chemical class 0.000 title claims description 19
- 238000001308 synthesis method Methods 0.000 title 1
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 44
- 229910021529 ammonia Inorganic materials 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 150000003863 ammonium salts Chemical class 0.000 claims description 16
- 238000010189 synthetic method Methods 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 13
- 150000002815 nickel Chemical class 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 150000001868 cobalt Chemical class 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- 159000000013 aluminium salts Chemical group 0.000 claims description 6
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 159000000003 magnesium salts Chemical class 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 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 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 19
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 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 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 60
- 229910052759 nickel Inorganic materials 0.000 description 22
- 239000000543 intermediate Substances 0.000 description 21
- 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 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 10
- 235000011130 ammonium sulphate Nutrition 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000000975 co-precipitation Methods 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 230000000536 complexating effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910016896 Ni0.82Co0.15Mg0.03(OH)2 Inorganic materials 0.000 description 2
- 241000220317 Rosa Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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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
A process for preparing the doped spherical nickelous hydroxide includes such steps as mixing 2-valence Ni salt and Co salt with ammonia water and ammoniunm salt to obtain complex solution, adding it along with the mixed solution of metallic salt and alkali solution into reactor, reaction while stirring, and washing the deposit. The resultant doped spherical nickelous hydroxide can be used to prepare the multi-element metallic oxide, which can be used to prepare the active positive electrode of Li-ion battery.
Description
[technical field]
The invention belongs to the high energy electrochemical field, be specifically related to the synthetic method and the lithium ion battery of ball-shaped mixed with/nickelnous hydroxide and multi-element metal oxide.
[background technology]
Present lithium ion battery extensive application on electron devices such as mobile telephone, laptop computer, portable audiovisual equipment, but its positive pole material of lithium cobalt acid (LiCoO
2) but because resource problem and price rises steadily has limited the development of lithium ion battery.Therefore people are constantly striving to find suitable equivalent material always.Recently research is maximum is composite positive pole such as cobalt nickel manganese.The method that bibliographical information the most generally uses is coprecipitation method.This method is metal-salt wiring solution-forming by a certain percentage, and adds additive such as ammoniacal liquor and be used for controlling the oxyhydroxide crystallization velocity, generates precipitation with alkali reaction then.This method is that ammoniacal liquor is joined in the end liquid, after salts solution is added drop-wise in the end liquid, and Ni
2+, Co
2+Deng metal ion elder generation and ammonia (NH
3) complexing action takes place, generate X (NH
3) n
2+(n=1～6, X=Ni, Co) complex ion, concentration of metal ions reduces.Along with Ni
2+, Co
2+With OH
-Reaction generates precipitation of hydroxide and sharply reduces, M (NH
3) n
2+Discharge the metal ion of complexing, make the solution metal ion keep finite concentration.But the shortcoming of this method is: after saline solution adds on earth in the liquid, and ammonia (NH
3) and OH
-Exist simultaneously to contact, the competition effect takes place, because OH with metal ion
-Compare NH
3Easier of Ni
2+, Co
2+Plasma reaction, ammonia (NH
3) the very difficult effect of bringing into play crystallization control, the midbody particle microtexture is not advised, and size distribution compares broad.
Belgium five ore deposit companies think that the bigger cycle performance of material granule is less.Wu state very waits the people to studies show that the size-grade distribution of material especially charges and discharge cycle performance to loading capacity remarkable influence is arranged, size-grade distribution is wide more, its cycle performance is just poor more, because when broad particle distribution, its porosity difference, influence it and capillary action of electrolytic solution is made the impedance performance bigger, when charging to limiting potential, the Li of large particle surface
+Can excessively take off embedding and destroy its hierarchical structure, so be unfavorable for cycle performance.
[summary of the invention]
The objective of the invention is to deficiency at above method, propose a kind of narrower particle size distribution, the ball-shaped mixed with/nickelnous hydroxide of good cycle and the synthetic method of multi-element metal oxide reach the lithium ion battery that adopts described multi-element metal oxide in the preparation of positive electrode material.
The technical scheme that realizes above-mentioned purpose is:
A kind of synthetic method of ball-shaped mixed with/nickelnous hydroxide 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 mixing solutions of the formed complex solution of step 1) and metal-salt and alkali lye and stream again, stir and generate described ball-shaped mixed with/nickelnous hydroxide precipitation, foreign ion is removed in washing.
Preferably: described metal-salt is selected from aluminium salt or magnesium salts or both mixtures.Described aluminium salt, magnesium salts be nitrate or acetate preferably.
Preferably: ammonia concn is 0.1～1mol/L in the described step 1), and ammonium salt concentration is 0.02～0.25mol/L.The mol ratio of ammoniacal liquor and ammonium salt is 4: 1～5: 1, ammonium salt employing and nickel salt, the salt that the cobalt salt acid group is identical.
Preferably: nickel salt and cobalt salt are vitriol, nitrate, chlorate or acetate, and alkali lye is NaOH or KOH, and the summation of nickel salt, cobalt salt, doped metal salt and the mol ratio of alkali lye are 1: 2.1～1: 2.4.
Preferably: also be added with end liquid in the described reaction vessel, end liquid is the mixing buffered soln 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.Ammonia concn in the end liquid is half of the ammonia concn described in the step 1) preferably.Stirring velocity is preferably 100～600r/min.
Be purpose of the present invention, a kind of preparation method of multi-element metal oxide also be provided, that is, will adopt aforesaid method synthetic ball-shaped mixed with/nickelnous hydroxide precipitation drying after, mix with lithium hydroxide, make finished product through high temperature sintering.
Preferably: the mol ratio of each metallic element sum in the described ball-shaped mixed with/nickelnous hydroxide (when metal-salt is when being selected from aluminium salt or magnesium salts or both mixtures, to be Ni, Co, Al sum or Ni, Co, Mg sum or Ni, Co, Al, Mg sum) and monohydrate lithium hydroxide be 1: 1.02～: 1.07; The high temperature sintering temperature is 700～800 ℃, and sintering time is 12～24 hours.
The present invention also provides a kind of lithium-ion secondary cell, contains the multi-element metal oxide that makes according to above-mentioned preparation method in its positive electrode active materials.
Adopt technique scheme, in conjunction with the following embodiment that will describe in detail, beneficial technical effects of the present invention is: 1) carry out metal ion mixing when generating ball nickel intermediate, make doped metal ion in liquid phase, form more uniform mixed hydroxides intermediary material with nickel, cobalt, this kind intermediate is in high-temperature sintering process, dopant ion can better enter the space of material structure cell, and the raising stratiform is taken off the embedding stability of structure, suppresses or slow down the phase transformation in the charge and discharge process; 2) when the preparation ball-shaped mixed with/nickelnous hydroxide, because before co-precipitation, first nickel salt, cobalt salt with divalence mixes the formation complex solution, and (ammonium salt and ammonia can form the buffered soln about pH=7 with ammoniacal liquor, ammonium salt, precipitation can not appear in complex solution, main purpose is that cobalt is not precipitated), mixing solutions with complex solution and doped metal salt and alkali lye also reacts in the stream adding reaction vessel again, generation ball-shaped mixed with/nickelnous hydroxide precipitation has effectively been avoided the direct adding of alkali lye to cause particle to be difficult to grow up and has been formed the spheric problem; 3) owing to be that complex solution and saline and alkaline mixed solution are and stream adds generation ball-shaped mixed with/nickelnous hydroxide precipitation in the reaction vessel, 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 the speed and the even particle size of generation ball-shaped mixed with/nickelnous hydroxide in the reaction vessel, can effectively control the size of intermediate, make synthetic intermediate narrower particle size distribution; 4) owing to liquid at the bottom of the mixing buffered soln 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 buffered soln can to guarantee to react the fluctuation of pH value when beginning very little; 5) use this method synthetic multi-element metal oxide cycle performance better; 6) synthetic intermediate tap density is bigger, helps industrialization.
The present invention is described in further detail below in conjunction with the drawings and specific embodiments.
[description of drawings]
Fig. 1 is the sreen analysis figure of a kind of ball-shaped mixed with/nickelnous hydroxide (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 scanning electron microscope (SEM) photographs.
The first charge-discharge curve of the battery that the multi-element metal oxide that Fig. 4 is to use product to make is made.
The cycle performance curve of the battery that the multi-element metal oxide that Fig. 5 is to use product to make is made.
[embodiment]
The invention provides a kind of synthetic method of ball-shaped mixed with/nickelnous hydroxide, comprise step 1): nickel salt, the cobalt salt with divalence mixes the formation complex solution with ammoniacal liquor, ammonium salt earlier; With step 2): mixing solutions and stream with the formed complex solution of step 1) and metal-salt and alkali lye add in the reaction vessel, stir and generate described ball-shaped mixed with/nickelnous hydroxide precipitation, and foreign ion is removed in washing.The ball-shaped mixed with/nickelnous hydroxide that makes (hereinafter to be referred as doping ball nickel) can be represented with such chemical formula: Ni
xCo
yM
(l-x-y)(OH)
n, wherein the M representative is mixed with the metallic element in the metal-salt, can be Al, Mg or their mixture.Adopt the above-mentioned ball-shaped mixed with/nickelnous hydroxide that makes as intermediate, can further prepare multi-element metal oxide, that is, will adopt aforesaid method synthetic doping ball nickel precipitation drying after, mix with lithium hydroxide, make finished product through high temperature sintering.The multi-element metal oxide that obtains can be used for making the positive electrode active materials of lithium ion battery.With specific embodiment in detail realization of the present invention and effect are described in detail below.
Embodiment one: doping ball nickel intermediate Ni
0.75Co
0.10Al
0.15(OH)
n(method one)
Above-mentioned doping ball nickel intermediates preparation:, add in the 40L reactor Ni with NaOH that has added Tai-Ace S 150 and stream with the complexing saline solution of single nickel salt, rose vitriol and ammoniacal liquor, ammonium sulfate
2+And Co
2+Mol ratio be 0.75: 0.10, total salt concn is 0.85mol/L, ammonia concentration is 0.8mol/L, ammonium sulfate concentrations is 0.18mol/L, NaOH concentration is 2.3mol/L, Tai-Ace S 150 concentration is 0.15mol/L, end liquid is the mixing solutions of ammonia and ammonium sulfate, and ammonia concentration is 0.4mol/L, and ammonium salt concentration is 0.09mol/L, end liquid consumption stirs just to mix with stirring arm and is as the criterion, control feed rate 1L/h, 50 ℃ of temperature of reaction, pH value 11.5, stirring velocity 600r/min, co-precipitation obtains bottle-green ball nickel intermediate Ni
0.75Co
0.10Al
0.15(OH)
nAgeing 2h removes SO 5～7 times with distilled water wash
4 2-, obtain the precursor material after 12 hours ball millings of baking are crossed solarization in 60 ℃ of baking ovens.
Product with the present embodiment preparation carries out structure and performance characterization by following means: adopt X-ray diffractometer (XRD) to determine the particulate thing mutually, utilize the shape and size of scanning electron microscope (SEM) direct viewing product.
According to shown in Figure 1, median size is 10 μ m, and the size distribution of this product is narrow, illustrates that the particle grain size size is more even.
According to the determined product particle thing of Fig. 2 phase XRD spectra, there are not assorted peak in position and number from diffraction peak, show that doping does not bring other dephasigns, and this feature shows that also product has regular laminate structure.
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.
Embodiment two: doping ball nickel intermediate Ni
0.75Co
0.10Al
0.15(OH)
n(method two)
Embodiment one is identical for this embodiment method fundamental sum, and nickel salt, cobalt salt and ammonium salt and the aluminium salt of different is present embodiment are acetate, and alkali is KOH, and the speed of stirring is 300r/min, and co-precipitation obtains bottle-green ball nickel intermediate Ni
0.75Co
0.10Al
0.15(OH)
nAgeing 2h removes acetate ion 5～7 times with distilled water wash, obtains the precursor material after 12 hours ball millings of baking are crossed solarization in 60 ℃ of baking ovens.
Embodiment three: doping ball nickel intermediate Ni
0.75Co
0.10Al
0.15(OH)
n(method three)
Embodiment one is identical for this embodiment method fundamental sum, and the ammonia concentration of different is present embodiment is 1mol/L, and ammonium sulfate concentrations is 0.25mol/L, and ammonia concentration is 0.5mol/L in the end liquid.Co-precipitation obtains bottle-green ball nickel intermediate Ni
0.75Co
0.10Al
0.15(OH)
n
Embodiment four: doping ball nickel intermediate Ni
0.75Co
0.10Al
0.15(OH)
n(method four)
Embodiment one is identical for this embodiment method fundamental sum, the ammonia concentration of different is present embodiment is 0.1mol/L, ammonium sulfate concentrations is 0.02mol/L, and ammonia concentration is 0.05mol/L in the end liquid, and stirring velocity obtains bottle-green ball nickel intermediate Ni for the 100r/min co-precipitation
0.75Co
0.10Al
0.15(OH)
n
Embodiment five: doping ball nickel intermediate Ni
0.82Co
0.15Al
0.03(OH)
n
Above-mentioned doping ball nickel intermediates preparation: present embodiment and embodiment one difference are: x=0.82, y=0.15 are Ni
2+And Co
2+Mol ratio be 0.82: 0.15, total salt concn is 0.97mol/L, the mol ratio of nickel cobalt and aluminium is 0.97: 0.03, other condition and preparation method are with embodiment one.
Embodiment six: doping ball nickel intermediate Ni
0.82Co
0.15Mg
0.03(OH)
2
Above-mentioned doping ball nickel intermediates preparation:, add in the 40L reactor Ni with NaOH and stream with the complexing saline solution of single nickel salt, rose vitriol, magnesium nitrate and ammoniacal liquor, ammonium sulfate
2+, Co
2+And Mg
2+Mol ratio be 0.82: 0.15: 0.03, total salt concn is 1mol/L, ammonia concentration is 0.8mol/L, ammonium sulfate concentrations is 0.4mol/L, and NaOH concentration is 2.4mol/L, and end liquid is the mixing solutions of ammonia and ammonium sulfate, ammonia concentration is 0.4mol/L, ammonium salt concentration is 0.09mol/L, and end liquid consumption stirs just to mix with stirring arm and is as the criterion, control feed rate 1L/h, 50 ℃ of temperature of reaction, pH value 11.5, stirring velocity 600r/min, co-precipitation obtains bottle-green spherical doping polyoxide Ni
0.82Co
0.15Mg
0.03(OH)
2
Embodiment seven: doping ball nickel intermediate Ni
0.82Co
0.15Al
0.02Mg
0.01(OH)
n
Above-mentioned intermediates preparation: the difference of present embodiment and embodiment seven is to change doping metals magnesium into aluminium and magnesium, the mol ratio of mixing Ni2+, Co2+, Al3+ and Mg2+ in the saline solution is 0.82: 0.15: 0.02: 0.01, total salt concn is 1mol/L, ammonia concentration is 0.4mol/L, and ammonium sulfate concentrations is 0.72mol/L.Saline solution and NaOH and stream add in the 40L reactor, NaOH concentration is 2.3～2.4mol/L, end liquid is the mixing solutions of ammonia and ammonium sulfate, and ammonia concentration is 0.2mol/L, and ammonium salt concentration is 0.09mol/L, end liquid consumption stirs just to mix with stirring arm and is as the criterion, control feed rate 1L/h, 50 ℃ of temperature of reaction, pH value 11.5, stirring velocity 600r/min, co-precipitation obtains bottle-green spherical doping polyoxide Ni
0.82Co
0.15Al
0.02Mg
0.01(OH)
n, ageing 2h removes SO42-5～7 times with distilled water wash, obtains the precursor material after 12 hours ball millings of baking are crossed solarization in 60 ℃ of baking ovens.Accurately measure its moisture, according to Ni
0.82Co
0.15Al
0.02Mg
0.01(OH)
nWith the mol ratio of LiOH be 1: 1.06, the crucible of packing into after ball milling mixes places resistance furnace with 5 ℃ temperature rise rate to 250 ℃, constant temperature 2h, continue to be warming up to 700 ℃ of constant temperature 12h then, treat that temperature reduces to below 200 ℃, take out crucible, ball mill pulverizing can obtain the anode material for lithium-ion batteries of heavy body, high voltage withstanding, good cycle.
Embodiment eight: multi-element metal oxide synthetic
With embodiment one synthetic material according to Ni
0.75Co
0.10Al
0.15(OH)
nWith the mol ratio of LiOH be 1: 1.06, the crucible of packing into after ball milling mixes places resistance furnace with 5 ℃ temperature rise rate to 250 ℃, constant temperature 2h, continue to be warming up to 700 ℃ of constant temperature 12h then, treat that temperature reduces to below 200 ℃, take out crucible, ball mill pulverizing can obtain the multi-element metal oxide of heavy body, high voltage withstanding, good cycle.
Adopt this multi-element metal oxide routinely program make the buckle type lithium-ion battery, its chemical property is detected.
According to Fig. 4 first charge-discharge curve as can be seen, the product that makes is high voltage withstanding, and charging can be to 4.5V, and safety performance is good.Initial charge specific storage 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 competent lithium source for negative terminal surface forms the SEI film.Capability retention is all more than 99% in the circulation afterwards, and 100 specific storagies that circulate still remain on more than the 120mAh/g.
This shows that multi-element metal oxide of the present invention is a kind of anode material for lithium-ion batteries with high conduction performance and cycle performance.
Claims (12)
1, a kind of synthetic method of ball-shaped mixed with/nickelnous hydroxide 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 mixing solutions of the formed complex solution of step 1) and metal-salt and alkali lye and stream again, stir and generate described ball-shaped mixed with/nickelnous hydroxide precipitation, foreign ion is removed in washing.
2, the synthetic method of ball-shaped mixed with/nickelnous hydroxide according to claim 1 is characterized in that: described metal-salt is selected from aluminium salt or magnesium salts or both mixtures.
3, the synthetic method of ball-shaped mixed with/nickelnous hydroxide according to claim 2 is characterized in that: described aluminium salt, magnesium salts are nitrate or acetate.
4, according to the synthetic method of any described ball-shaped mixed with/nickelnous hydroxide of claim 1～3, it is characterized in that: described ammonia concn is 0.1～1mol/L, and ammonium salt concentration is 0.02～0.25mol/L.
5, the synthetic method of ball-shaped mixed with/nickelnous hydroxide according to claim 4 is characterized in that: the mol ratio of described ammoniacal liquor and ammonium salt is 4: 1～5: 1, ammonium salt employing and nickel salt, the salt that the cobalt salt acid group is identical.
6, according to the synthetic method of any described ball-shaped mixed with/nickelnous hydroxide of claim 1～3, it is characterized in that: also be added with end liquid in the described reaction vessel, end liquid is the mixing buffered soln 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.
7, according to the synthetic method of any described ball-shaped mixed with/nickelnous hydroxide of claim 1～3, it is characterized in that: described nickel salt and cobalt salt are vitriol, nitrate, chlorate or acetate, and alkali lye is NaOH or KOH.
8, the synthetic method of ball-shaped mixed with/nickelnous hydroxide according to claim 7 is characterized in that: the summation of described nickel salt, cobalt salt, metal-salt and the mol ratio of alkali lye are 1: 2.1～1: 2.4.
9, according to the synthetic method of any described ball-shaped mixed with/nickelnous hydroxide of claim 1～3, it is characterized in that: stirring velocity is 100～600r/min.
10, a kind of preparation method of multi-element metal oxide is characterized in that: will mix with lithium hydroxide according to after the described method synthetic of above-mentioned any one claim ball-shaped mixed with/nickelnous hydroxide precipitation drying, make finished product through high temperature sintering.
11, the preparation method of multi-element metal oxide according to claim 10 is characterized in that: the mol ratio of each metallic element sum and monohydrate lithium hydroxide is 1: 1.02～1: 1.07 in the described ball-shaped mixed with/nickelnous hydroxide.
12, a kind of lithium-ion secondary cell contains the multi-element metal oxide that makes according to the described preparation method of claim 10 in its positive electrode active materials.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107531510A (en) * | 2015-04-28 | 2018-01-02 | 住友金属矿山株式会社 | Aluminium coats nickel and cobalt containing complex hydroxide and manufacture method, non-aqueous electrolyte secondary battery and positive active material and manufacture method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107531510A (en) * | 2015-04-28 | 2018-01-02 | 住友金属矿山株式会社 | Aluminium coats nickel and cobalt containing complex hydroxide and manufacture method, non-aqueous electrolyte secondary battery and positive active material and manufacture method |
| CN107531510B (en) * | 2015-04-28 | 2020-03-24 | 住友金属矿山株式会社 | Aluminum-coated nickel-cobalt-containing composite hydroxide and method for producing same, nonaqueous electrolyte secondary battery, positive electrode active material, and method for producing same |
| US10858265B2 (en) | 2015-04-28 | 2020-12-08 | Sumitomo Metal Mining Co., Ltd. | Aluminum-coated nickel cobalt containing composite hydroxide and method for manufacturing same, cathode active material for non-aqueous electrolyte secondary battery and method for manufacturing same, and non-aqueous electrolyte secondary battery |
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