CN100423329C - Spherical nickel hydroxide surface modification method - Google Patents
Spherical nickel hydroxide surface modification method Download PDFInfo
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- CN100423329C CN100423329C CNB2004100229356A CN200410022935A CN100423329C CN 100423329 C CN100423329 C CN 100423329C CN B2004100229356 A CNB2004100229356 A CN B2004100229356A CN 200410022935 A CN200410022935 A CN 200410022935A CN 100423329 C CN100423329 C CN 100423329C
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- nickel hydroxide
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a method for modifying the surface of nickel hydroxide and a modification technology, wherein the method 1 comprises the steps of adding a nickel sulfate solution, an ammonia water solution and a sodium hydroxide solution with certain concentrations into slurry containing a spherical nickel hydroxide matrix, reacting at a specific temperature, a specific pH value and a specific time, aging the slurry for a certain time after the reaction is finished, washing, filtering and drying to obtain the nickel hydroxide with a fine crystal structure and a compact and smooth coating layer. Method 2 differs from method 1 in that the reactants added are a metal complex solution and a nickel hydroxide solution, and the obtained nickel hydroxide is a coated layer having a desired coated metal component. Method 3 method 1 and method 2 were used in series to obtain nickel hydroxide with a double coating. The method improves the specific energy of the nickel hydroxide, reduces the production cost, enlarges the application range of the nickel hydroxide and improves the high-temperature charging efficiency, and the prepared nickel hydroxide not only can be suitable for small batteries, but also can meet the high-temperature performance requirement of the anode material of the power battery.
Description
Technical field:
The invention belongs to the power battery anode material preparation field, relate in particular to method and modification technology to the finishing of nickel hydroxide, the good nickel hydroxide of preparation high-temperature behavior is to satisfy the needs of electrokinetic cell to the positive electrode active materials performance requirement.
Background technology:
As everyone knows, the nickel electrode battery capacity all is to adopt the positive electrode capacity controlling Design, and the electrical property of positive electrode active materials nickel hydroxide is determining battery performance to a great extent.Utilize surface modification technology to improve and improve the chemical property of nickel hydroxide, be confirmed technically already and use.US6,083,642 (July4,2000) and CN1089196C can be described as the representative in the relevant nickel hydroxide surface modification technology patent documentation.The former is coated on the nickel hydroxide particle surface with cobalt/cobalt oxide, and cobalt wherein mainly is γ-CoOOH form, and the average oxidation state of cobalt is greater than 3, and the characteristics of this nickel hydroxide are that the active matter utilance is higher, and the capacity restoration rate after overdischarge and short circulation is higher; The latter adopts a kind of dynamic integral feed way, coat the hydroxide of cobalt at nickel hydroxide surface, in heat treatment process subsequently, make that the valence state of cobalt transforms in the coating layer, the main feature of this technology is to generate a transition zone between coating layer and former spherolite surface, coating layer does not closely come off, and covered effect is better.But, because coating valence state that the unicity of composition, a large amount of cobalt coat cobalt in the higher and Overmolded process of costs, to be difficult for accurately control etc. former thereby influence product quality, tap density, cost and consistency, the scope of application, particularly the high temperature charge-discharge performance of battery is poor, and 50 ℃ of high-temperature charging efficient have only about 80% of normal temperature.As electrokinetic cell because the particularity of its purposes and the complexity of environment for use, to it chemical property and the requirement of processing performance all than common batteries height.The performance index of electrokinetic cell are mainly specific energy, specific power, adverse circumstances applicability, fail safe, consistency and the cost etc. of battery.Particularly electrokinetic cell requires higher to the high temperature charge-discharge performance of nickel hydroxide.Therefore, the nickel hydroxide of the above-mentioned type surface modification also is only applicable to compact battery, and is difficult to satisfy the high-temperature behavior requirement as power battery anode material.
Summary of the invention:
One of purpose of the present invention is to optimize the crystal structure of nickel hydroxide coating layer, improves specific energy, the tap density of nickel hydroxide, reduces production costs.
Two of purpose is to optimize to coat composition, improves covered effect, enlarges the scope of application of nickel hydroxide, improves high-temperature charging efficient, and Zhi Bei nickel hydroxide had both gone for compact battery thus, also can satisfy the high-temperature behavior requirement of power battery anode material.
For achieving the above object, one of technical scheme of the present invention is: make raw material with the slip that contains the ball-shape nickel hydroxide parent, under stirring condition, slurry temperature 30-80 ℃, and the continuous concentration that adds of stream is respectively the nickel sulfate solution that 0.5～2mol/L contains Co, Zn, 1～5mol/L ammonia spirit and 2～6mol/L sodium hydroxide solution, pH value is 11.2-11.8, reaction time 1-6 hour, make that the coating layer quality of the nickel hydroxide in the slip is 3～16% of original parent ball-shape nickel hydroxide quality, slip ageing 1-3 hour; Washing, filtration, drying obtain having the composition nickel hydroxide product identical with parent of trickle crystal structure, tight smooth coating layer.
The nickel sulfate solution of the such scheme one described Co of containing, Zn is mixed by the soluble-salt of Ni, Co, Zn, and wherein the mol ratio of Ni: Co: Zn is 100: 0-3: 0-6.
Two of technical scheme of the present invention is: make raw material with the slip that contains the ball-shape nickel hydroxide parent, under stirring condition, slurry temperature 30-80 ℃, also stream adds the sodium hydroxide solution that concentration is respectively 0.1-1mol/L metal network and solution and 2-6mol/L continuously, pH value is 10-12, reaction time 2-8 hour, make that nickel hydroxide coating layer quality is the 2-10% of parent ball-shape nickel hydroxide quality in the slip; Slip ageing 1-3 hour, washing, filtration, drying obtain having the nickel hydroxide product of the coating layer of required clad metal composition.
Such scheme two described metal networks and solution are mixed by soluble-salt solution and the complexing agent for the treatment of clad metal, wherein add and treat that the mol ratio of clad metal ion and complexing agent is 1: 0.1-1, coating layer treat the hydroxide of clad metal or treat other compounds of clad metal.Treat clad metal soluble-salt solution metal ion can be Al, Mg, Ba, Ca, Sr,, in Mn, Co, Ti, Zn, In and the rare earth element one or more, complexing agent can be one or more in ammoniacal liquor, ammonium salt, acetic acid, citric acid (or its salt), EDTA (or its salt) or the tartrate.
Three of technical scheme of the present invention is: such scheme one and scheme two described method series connection are used, at first once coat, it is scheme one described nickel hydroxide surface method of modifying, make ball-shape nickel hydroxide parent surface generate a coating layer of nickel hydroxide, carry out secondary according to the nickel hydroxide surface method of modifying described in the scheme two again and coat with trickle crystal structure.Promptly make raw material with the parent slip of the nickel hydroxide that once coats, at the secondary coating layer of parent ball shape nickel hydroxide surface regeneration special metal compound, the slip ageing through washing, filtration, drying, obtained having the nickel hydroxide of double-contracting coating after 1-3 hour.
The three described reaction time that once coat of such scheme are 0.5-1.5 hour, make that the quality of a coating layer is the 2-6% of original parent ball-shape nickel hydroxide quality; The reaction time that secondary coats is 0.5-4 hour, makes that the quality of secondary coating layer is the 2-6% of original parent ball-shape nickel hydroxide quality.
The slip that contains the ball-shape nickel hydroxide parent in above-mentioned three schemes can be the end of a period slip that controlled precipitated crystal method is produced ball shape nickel hydroxide surface technology, also can be the slip that forms with ball-shape nickel hydroxide and deionized water modulation, the concentration of ball-shape nickel hydroxide be 80-120g/L in the slip.
The nickel hydroxide product that adopts one of technique scheme to produce owing to coated the nickel hydroxide coating layer of trickle crystal structure, has therefore been optimized the nickel hydroxide surface micro-structural, help improving nickel hydroxide specific energy, tap density, reduce production costs.
Adopt the two nickel hydroxide products of producing of technique scheme, owing to coated the coating layer of special metal compound, therefore optimized the chemical composition of nickel hydroxide surface, make coating layer more evenly, combine with the parent nickel hydroxide securely, help improving the high-temperature electrochemical properties of nickel hydroxide, make it be more suitable for being applied to electrokinetic cell.
Adopt the three nickel hydroxide products of producing of technique scheme,, improved covered effect comprehensively, thereby helped improving the comprehensive electrochemical of nickel hydroxide owing to optimized the crystal structure and the chemical composition of nickel hydroxide coating layer.
Specific embodiment: the embodiment that adopts the nickel hydroxide product of one of technical scheme of the present invention production:
Embodiment 1: use NiSO
4.6H
2O, CoSO
4.7H
2O, ZnSO
4.7H
2The O preparation contains the nickelous sulfate mixed solution of Co, Zn, wherein NiSO
4Concentration be 2mol/L, Ni: Co: Zn=100: 2.7: 4.9 (mol ratio); Ammonia spirit and the 5mol/L sodium hydroxide solution of preparation 12mol/L.Be modulated into the slip that volume is 25L with ball-shape nickel hydroxide and deionized water, the concentration of ball-shape nickel hydroxide is 100g/L in the slip, insert in the multifunctional reactor that dischargeable capacity is 30L, with peristaltic pump with above-mentioned nickelous sulfate mixed solution, ammonia spirit, the continuous respectively also stream of sodium hydroxide solution is pumped in the reactor, mixing speed is 800rpm, the pH that controls reaction system by the flow of regulating the sodium hydroxide solution that adds is 11.5 ± 0.02, reaction temperature is 50 ± 1 ℃. discharge supernatant continuously by solid-liquid separator, and solid-state nickel hydroxide is not discharged, the operation reaction stopped charging after 1.6 hours continuously, slip keeps 50 ℃ of ageings after 3 hours, the pH that directly ends cleaning solution with deionized water cyclic washing nickel hydroxide slip is neutral, and till barium salt detection sulfate radical-free, clear groove is discharged the nickel hydroxide slip, and in Buchner funnel, carry out Separation of Solid and Liquid, it is following dry 4 hours at 120 ℃ that the solid product that separates is put into drying box, obtain having the nickel hydroxide product of the nickel hydroxide coating layer of trickle crystal structure, the mass percent of coating layer nickel hydroxide is 6% of a parent nickel hydroxide quality, and the nickel hydroxide sample of this modification is designated as A1.
Embodiment 2: controlling reaction time is to stop charging after 2.4 hours, other condition is identical with embodiment 1, obtain having the nickel hydroxide product of the nickel hydroxide coating layer of trickle crystal structure, the mass percent of coating layer nickel hydroxide is 9% of a parent nickel hydroxide quality, and the nickel hydroxide sample of this modification is designated as A2.
Embodiment 3: controlling reaction time is to stop charging after 4.2 hours, other condition is identical with embodiment 1, obtain having the nickel hydroxide product of the nickel hydroxide coating layer of trickle crystal structure, the mass percent of coating layer nickel hydroxide is 16% of a parent nickel hydroxide quality, and the nickel hydroxide sample of this modification is designated as A3.
Adopt two of technical scheme of the present invention to produce the embodiment of nickel hydroxide product:
Embodiment 4: preparation contains and remains the mixing complex solution of clad metal Co, Y, uses CoSO
47H
2O, Y (NO)
37H
2O and, the mixing complex solution of citric acid preparation Co, Y, Co wherein
2+Concentration is 0.68mol/L, Y
3+Concentration be 0.31mol/L, the concentration of citric acid is 0.4mol/L, preparation 5mol/L sodium hydroxide solution.Insert in the multifunctional reactor with the ball-shape nickel hydroxide slip described in the embodiment 1, with peristaltic pump with above-mentioned Co, the mixing complex solution of Y, the continuous respectively also stream of sodium hydroxide solution is pumped in the reactor, mixing speed is 600rpm, the pH that controls reaction system by the flow of regulating the sodium hydroxide solution that adds is 11.2 ± 0.02, reaction temperature is 50 ± 1 ℃. adopt solid-liquid separator to discharge supernatant continuously, and solid-state nickel hydroxide is not discharged, the operation reaction stopped charging after 2 hours continuously, slip continues to keep 50 ℃ of ageings after 3 hours, the pH that directly ends cleaning solution with deionized water cyclic washing nickel hydroxide slip is neutral, and till barium salt detection sulfate radical-free, clear groove is discharged the nickel hydroxide slip, and in Buchner funnel, carry out Separation of Solid and Liquid, it is following dry 4 hours at 120 ℃ that the solid product that separates is put into drying box, obtain having Co, the nickel hydroxide product of Y hydroxide coating layer, coating layer cobalt hydroxide mass percent is 1.6% of a parent nickel hydroxide quality, the mass percent of coating layer yttrium hydroxide is 1.1% of a parent nickel hydroxide quality, and the nickel hydroxide sample of this modification is designated as B1.
Embodiment 5: controlling reaction time is to stop charging after 4 hours, other condition is identical with embodiment 4, obtain having Co, the nickel hydroxide product of Y hydroxide coating layer, coating layer cobalt hydroxide mass percent is 3.2% of a parent nickel hydroxide quality, the mass percent of coating layer yttrium hydroxide is 2.2% of a parent nickel hydroxide quality, and the nickel hydroxide sample of this modification is designated as B2.
Embodiment 6: controlling reaction time is to stop charging after 6 hours, other condition is identical with embodiment 4, obtain having Co, the nickel hydroxide product of Y hydroxide coating layer, coating layer cobalt hydroxide mass percent is 4.8% of a parent nickel hydroxide quality, the mass percent of coating layer yttrium hydroxide is 3.4% of a parent nickel hydroxide quality, and the nickel hydroxide sample of this modification is designated as B3.
Embodiment 7: preparation contains and remains clad metal Co complex solution, uses CoSO
47H
2O and citric acid preparation cobalt complex solution, Co wherein
2+Concentration is that the concentration of .0.68mol/L, citric acid is 0.3mol/L, controlling reaction time is to stop charging after 6.4 hours, other condition is identical with embodiment 4, obtain having the nickel hydroxide product of cobalt hydroxide coating layer, coating layer cobalt hydroxide mass percent is 5% of a parent nickel hydroxide quality, and the nickel hydroxide sample of this modification is designated as B4.
Adopt three of technical scheme of the present invention to produce the embodiment of nickel hydroxide product:
Embodiment 8: the above-mentioned two kinds of technical schemes of Joint Implementation, at first once coat, promptly implement once to coat by the embodiment 1 identical process of implementing one of technical scheme of the present invention, the control reaction stopped charging after 0.8 hour, other condition is identical with embodiment 1, generate coating layer of nickel hydroxide on ball-shape nickel hydroxide parent surface with trickle crystal structure, the mass percent of a coating layer of nickel hydroxide is 3.0% of a parent nickel hydroxide quality, carrying out secondary by two embodiment 5 identical processes of technical scheme of the present invention again coats, promptly make raw material with the parent slip of the nickel hydroxide that once coats, the secondary coating layer of parent ball shape nickel hydroxide surface regeneration special metal compound, in the secondary coating layer of special metal compound, the mass percent of cobalt hydroxide coating layer is 3.2% of a parent nickel hydroxide quality, the mass percent of yttrium hydroxide coating layer is 1.8% of a parent nickel hydroxide quality, and this modification nickel hydroxide sample with double-contracting coat structure is designated as C1.
Nickel hydroxide electrical property detection method: adopt simulated battery pole piece method to detect the nickel hydroxide electrical property.
The nickel electrode of simulated battery is made and the Performance Detection condition: each 0.2g of finishing ball-shape nickel hydroxide sample that takes by weighing parent ball-shape nickel hydroxide sample and embodiment 1-8 respectively, each adds the 0.4g nickel powder, after nickel hydroxide and nickel powder mixed, according to this each biased sample is being placed particular manufacturing craft, under the pressure of 6Mpa, 1 minute aftershaping of static pressure obtains the positive plate that diameter is 1cm (work electrode), and each sample is made three positive plates (nickel electrode).The Performance of nickel electrode testing process is: with the metallic nickel sheet is negative pole, mercuric oxide electrode (HgO/Hg/6mol/LKOH) is a reference electrode, mixed solution with the LiOH of the KOH of 6mol/L and 15g/L is an electrolyte, a positive plate and two negative plates and a reference electrode are formed three electric pole type simulated batteries, fill with electrolyte in the battery, electrode soaks in electrolyte after 12 hours and carries out charge-discharge test, the instrument that adopts is that the DC-5 battery that the square Electronics Co., Ltd in Shanghai produces then tries instrument, by certain multiplying power (0.2C), under uniform temperature (as room temperature or 50 ℃), carry out charge-discharge test, the system that discharges and recharges is ended for being discharged to 0.1V after overcharging 50%, 6 circulations of general normal temperature test, high temperature is 3～6 circulations, gets its stable circulation value and calculates specific discharge capacity.
The electrical property of above-mentioned different hydro nickel oxide sample and the testing result of tap density are as follows:
Claims (4)
1. ball shape nickel hydroxide surface method of modifying, it is characterized in that: make raw material with the slip that contains the ball-shape nickel hydroxide parent, 30-80 ℃ of control slurry temperature, and the continuous concentration that adds of stream is respectively the nickel sulfate solution that 0.5-2mol/L contains Co, Zn, 1-5mol/L ammonia spirit and 2-6mol/L sodium hydroxide solution, pH value is 11.2-11.8, reaction time 1-6 hour, make that the coating layer quality of the nickel hydroxide in the slip is the 3-16% of original parent ball-shape nickel hydroxide quality, slip ageing 1-3 hour; Washing, filtration, drying obtain having the composition nickel hydroxide product identical with parent of trickle crystal structure, tight smooth coating layer.
2. ball shape nickel hydroxide surface method of modifying according to claim 1 is characterized in that: the nickel sulfate solution that contains Co, Zn is mixed by the soluble-salt that contains Ni, Co, Zn, and wherein the mol ratio of Ni: Co: Zn is 100: 0-3: 0-6.
3. ball shape nickel hydroxide surface method of modifying, it is characterized in that: with ball-shape nickel hydroxide concentration is that the slip of 100g/L is made raw material, continuously and stream add to contain and remain mixing complex solution and the 5mol/L sodium hydroxide solution of clad metal Co, Y, this mixing complex solution CoSO
4.7H
2O, Y (NO)
3.7H
2O and citric acid preparation, wherein Co
2+Concentration is 0.68mol/L, Y
3+Concentration be 0.31mol/L, citric acid concentration is 0.4mol/L; Mixing speed is 600rpm, the pH that controls reaction system by the flow of regulating the sodium hydroxide solution that adds is 11.2 ± 0.02, reaction temperature is 50 ± 1 ℃, the operation reaction stops charging after 2 hours or 4 hours or 6 hours continuously, slip continues to keep 50 ℃ of ageings 3 hours, washing, filter, 120 ℃ dry 4 hours down, obtain having Co, the nickel hydroxide product of Y hydroxide coating layer.
4. nickel hydroxide surface method of modifying, it is characterized in that: nickel hydroxide surface method of modifying according to claim 1 carries out secondary again and coats after ball-shape nickel hydroxide parent surface generates a coating layer of the nickel hydroxide with trickle crystal structure; The secondary coating is to make raw material with the parent slip of the nickel hydroxide after once coating, 30-80 ℃ of control slurry temperature, continuously and stream to add the concentration that is mixed by one or more complexing agents in one or more and ammoniacal liquor, ammonium salt, acetic acid, citric acid, citrate or the tartrate treated in clad metal Al, Mg, Ba, Ca, Sr, Mn, Co, Ti, Zn, In, the rare earth element be the sodium hydroxide solution of 0.1-1mol/L metal network and solution and 2-6mol/L, pH value is 10-12; Once the reaction time of Bao Fuing is 0.5-1.5 hour, makes that the quality of a coating layer is the 2-6% of original parent ball-shape nickel hydroxide quality; Reaction time 0.5-4 hour of coating of secondary makes that the quality of secondary coating layer is the 2-6% of original parent ball-shape nickel hydroxide quality; Slip ageing 1-3 hour, washing, filtration, drying obtain having the nickel hydroxide of double-contracting coating.
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| CNB2004100229356A CN100423329C (en) | 2004-03-01 | 2004-03-01 | Spherical nickel hydroxide surface modification method |
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| CNB2004100229356A CN100423329C (en) | 2004-03-01 | 2004-03-01 | Spherical nickel hydroxide surface modification method |
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| CN100423329C true CN100423329C (en) | 2008-10-01 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320681C (en) * | 2005-05-31 | 2007-06-06 | 深圳市豪鹏科技有限公司 | Long time stored nickel-hydrogen battery and mfg. method thereof |
| CN102054987A (en) * | 2010-11-24 | 2011-05-11 | 安徽亚兰德新能源材料有限公司 | Spherical nickel hydroxide for high-temperature battery anode and preparation method thereof |
| CN102569782B (en) * | 2010-12-30 | 2015-09-09 | 河南科隆集团有限公司 | Cobalt-aluminum-doped nickel oxyhydroxide and preparation method thereof |
| CN102664266B (en) * | 2011-11-25 | 2015-04-22 | 安徽亚兰德新能源材料股份有限公司 | Method for preparing spherical nickel hydroxide by doping zinc, manganese and aluminum |
| CN103682324A (en) * | 2012-09-14 | 2014-03-26 | 江苏博力新能源有限公司 | Novel method for functionalizing beta-phase spherical nickel hydroxide surface layer |
| JP5626387B2 (en) * | 2012-10-25 | 2014-11-19 | 住友金属鉱山株式会社 | The evaluation method of the coating adhesiveness of the coating nickel hydroxide powder for alkaline secondary battery positive electrode active materials and a coating nickel hydroxide powder. |
| CN104218266A (en) * | 2014-09-05 | 2014-12-17 | 冯祖勇 | Preparation method of high-performance graphene-based NI-MH power battery |
| KR102386051B1 (en) * | 2016-06-14 | 2022-04-14 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Method for producing nickel-containing hydroxide |
| CN111041214B (en) * | 2019-12-23 | 2021-08-31 | 先进储能材料国家工程研究中心有限责任公司 | Method for preparing alpha spherical nickel by recycling waste zinc-containing nickel-hydrogen batteries |
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| JPH11111284A (en) * | 1997-09-11 | 1999-04-23 | Samsung Display Devices Co Ltd | Nickel hydroxide active material of double structure and nickel positive electrode using this |
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| CN1417877A (en) * | 2002-12-30 | 2003-05-14 | 清华大学 | Prepn of Y-containing spherical nickel hydroxide |
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2004
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Patent Citations (4)
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|---|---|---|---|---|
| JPH11111284A (en) * | 1997-09-11 | 1999-04-23 | Samsung Display Devices Co Ltd | Nickel hydroxide active material of double structure and nickel positive electrode using this |
| JP2000082463A (en) * | 1998-09-04 | 2000-03-21 | Sumitomo Electric Ind Ltd | Nickel positive electrode active material for alkaline battery and its manufacture |
| CN1089196C (en) * | 1999-05-21 | 2002-08-14 | 清华大学 | Process of surface cobalt-coating for high-density ball-shape nickel hydroxide |
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| Title |
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| Co(OH)2包覆的Ni(OH)2电化学性能研究. 丁万春，袁安保，张鉴清，曹楚南.电源技术，第24卷第4期. 2000 * |
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