CN101320805B - Preparation method of nickel-hydrogen battery and its anode material - Google Patents
Preparation method of nickel-hydrogen battery and its anode material Download PDFInfo
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- CN101320805B CN101320805B CN2008100683629A CN200810068362A CN101320805B CN 101320805 B CN101320805 B CN 101320805B CN 2008100683629 A CN2008100683629 A CN 2008100683629A CN 200810068362 A CN200810068362 A CN 200810068362A CN 101320805 B CN101320805 B CN 101320805B
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- 238000002360 preparation method Methods 0.000 title claims description 38
- 239000001257 hydrogen Substances 0.000 title abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 title abstract description 6
- 239000010405 anode material Substances 0.000 title description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 231
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 114
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 55
- 229910018916 CoOOH Inorganic materials 0.000 claims abstract description 44
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 claims description 46
- 230000004913 activation Effects 0.000 claims description 27
- 230000003647 oxidation Effects 0.000 claims description 22
- 229910018095 Ni-MH Inorganic materials 0.000 claims description 17
- 229910018477 Ni—MH Inorganic materials 0.000 claims description 17
- 230000004888 barrier function Effects 0.000 claims description 4
- 230000003442 weekly effect Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 54
- 238000004519 manufacturing process Methods 0.000 abstract description 31
- 239000000843 powder Substances 0.000 abstract description 28
- 230000015572 biosynthetic process Effects 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 49
- 238000003786 synthesis reaction Methods 0.000 description 46
- 238000012360 testing method Methods 0.000 description 33
- 230000008569 process Effects 0.000 description 29
- 230000000630 rising effect Effects 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 230000008859 change Effects 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229910002640 NiOOH Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- -1 hydrogen nickel oxide Chemical class 0.000 description 1
- VUFYPLUHTVSSGR-UHFFFAOYSA-M hydroxy(oxo)nickel Chemical compound O[Ni]=O VUFYPLUHTVSSGR-UHFFFAOYSA-M 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 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 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A nickel-hydrogen battery and a production method for positive pole material of the nickel-hydrogen battery are disclosed, the method comprises the following steps of: 1) production of the positive pole, at first, the surface of spherical nickel hydroxide as positive pole active substance is covered with a gamma-CoOOH covering layer, then the spherical nickel hydroxide whose surface is covered with the gamma-CoOOH is partially oxidized, average chemical valence of the nickel after oxidization is controlled as 2.08-2.20; 2) production of the negative pole, proportion of the capacitance of the negative pole to the capacitance of the positive pole is (1.15-1.25):1; 3) assembly for the negative pole, the positive pole and membrane; 4) formation of the battery, 0.05C-0.2C of current is adopted to activate the battery for 3 to 10 weeks with charge and discharge capacitances during each week being between 30% and 100%, and the current amount of the battery at the time of discharging in the first week is discharged to zero. The positive pole uses the partially-oxidized spherical nickel hydroxide whose surface is covered with the gamma-CoOOH, when the designed capacitance proportion of the positive and negative poles is fixed, the designed capacitance of the negative pole can be reduced correspondingly, powder applying amount of the negative pole is lessened, manufacturing cost of the battery is saved, and the battery is able to maintain the characteristics of long service life and resistance to overcharge.
Description
Technical field
The present invention relates to the battery manufacturing technology, specifically relate to a kind of preparation method of nickel-hydrogen battery positive pole material and adopt the preparation method of the Ni-MH battery of this positive electrode.
Background technology
During the Ni-MH battery design, guarantee that generally capacity of negative plates is excessive, let slip in the journey with crossing at over-charging of battery like this that negative pole can be eliminated the O of generation
2And H
2: when having guaranteed battery overcharge, can not cause inner pressure of battery to raise because of separating out oxygen, during battery over-discharge, negative pole can not be forced oxidation.The capacity of negative plates of Ni-MH battery is removed the part that is complementary with positive electrode capacity and is excessive part, and this part capacity is divided into two parts: charging idle capacity and discharge reserve capacity, the distribution of Ni-MH battery both positive and negative polarity capacity can be expressed as Fig. 1.In general, when the both positive and negative polarity capacity ratio was 1: 1.25, Capacity design can satisfy the requirement of long-life batteries.
When overcharging, anode generation oxygen evolution reaction, the oxygen of separating out arrives negative terminal surface through barrier film, and the charging idle capacity makes oxygen and the metal hydride generation recombination reaction that arrives negative terminal surface, therefore, can not cause inner pressure of battery to raise because separating out oxygen.
The discharge reserve capacity is formed by two parts.
First, the divalence cobalt in the positive pole just can not be reduced again, thereby when negative pole has formed with the divalence cobalt oxidation, fill the discharge reserve capacity that electric weight into equates after being oxidized to the trivalent cobalt after the activation first time.
The discharge reserve capacity of second portion forms when being oxidized to high price nickel by the nickelous in the positive pole.
The positive pole reaction of common Ni-MH battery is:
Charging Ni (OH)
2+ OH-→ NiOOH+H
2O+e
Discharge NiOOH+H
2O+e → Ni (OH)
2+ OH-
This is a kind of reversible reaction that between diatomic hydrogen nickel oxide and trivalent hydroxy nickel oxide, transforms each other, but this reaction is not a kind of completely reversibility reaction.In the actual use, battery, can not discharge fully during the discharge of high price nickel during to 1.0V with certain multiplying power discharging; The average valence of nickel is about 2.2 valencys in its discharging product; Be battery when being full of electricity, the nickel in the positive pole is converted into 3.2 valencys by 2.0 valencys, is converted into 2.2 valencys by 3.2 valencys during discharge; Rather than 2.0 valencys of initial condition; This just means that the electric weight between the nickel valency 2.0 to 2.2 is not emitted in the positive pole, has then formed the discharge reserve capacity that waits capacity at negative pole, and this a part of discharge reserve capacity does not work to discharging and recharging all.
Anodal control capacity is deferred in the Ni-MH battery design, the excessive design principle of negative pole designs; Often to sacrifice the negative pole excessive value of battery design in order to make high-capacity battery; Exchange the loading that bigger space increases positive active material for this; Increase the available capacity proportioning of both positive and negative polarity, but meanwhile because of the minimizing of the excessive quantity of negative pole can cause battery life-span, the decreased performance of aspect such as overcharge.Prepare a kind of long-life high-capacity battery,, must reduce the available capacity proportioning of both positive and negative polarity when capacity ratio one timing of both positive and negative polarity design.
Do not consider other capacitance loss; The initial valence state of nickel is 2.0 in the ball nickel that positive pole adopts; The capacity ratio of both positive and negative polarity design is 1: 1.4 o'clock; Battery discharge is to 1.0V, and the electric weight of not emitting in the positive pole is (2.2-2.0)/(3.2-2.0) * 100% ≈ 17% of positive electrode capacity, and the available capacity proportioning of both positive and negative polarity is 1: (1.4-0.17)=1: 1.23.
Do not consider other capacitance loss; The initial valence state of nickel is 2.2 in the ball nickel that positive pole adopts; The capacity ratio of both positive and negative polarity design is 1: 1.4 o'clock; Battery discharge is to 1.0V, and the electric weight of not emitting in the positive pole is (2.2-2.2)/(3.2-2.0) * 100% ≈ 0% of positive electrode capacity, and the available capacity proportioning of both positive and negative polarity is 1: (1.4-0)=1: 1.4
Therefore, can reduce the negative discharge idle capacity, be equivalent to reduce the effective capacity ratio of both positive and negative polarity, thereby improve the cycle performance of battery and the consumption of overcharging resisting performance or minimizing negative pole alloy through the initial valence state of regulating anodal nickel.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of nickel-hydrogen battery positive pole material; Regulate the discharge reserve capacity of negative pole through the chemical valence that improves anodal nickel; Thereby improve the cycle performance of battery and the consumption of overcharging resisting performance or minimizing negative pole alloy; The chemical synthesizing method that adopts the present invention to propose simultaneously can obtain normal discharge capacity.
Another object of the present invention is to propose a kind of preparation method who adopts the Ni-MH battery of above-mentioned positive electrode.
The objective of the invention is to be achieved through following technical scheme.
The characteristics of the method for preparing anode material of this Ni-MH battery are: will coat one deck γ-CoOOH cover layer as the ball shape nickel hydroxide surface of positive active material earlier; Ball-shape nickel hydroxide with coated gamma-CoOOH carries out partial oxidation again, and the average valence of the nickel after the controlled oxidation is 2.08～2.20.
Saidly coat the tectal process of one deck γ-CoOOH at ball shape nickel hydroxide surface and may further comprise the steps:
A) at the sub-compound that applies one deck cobalt on the ball-shape nickel hydroxide kernel: the CoSO4 solution that adds 10%-25% in the solution at ball-shape nickel hydroxide; Regulate pH value the sub-compound of Co is deposited on the ball-shape nickel hydroxide kernel, and drying obtains powder body material;
B) the described ball-shape nickel hydroxide that is coated with the low price cobalt compound is carried out oxidation; The sub-compound that coats cobalt above that is oxidized to γ-CoOOH: coat to the surface that the sprinkle weight ratio is the NaOH of the 30%-40% mass concentration of 5%-8% in the ball-shape nickel hydroxide powder of sub-compound of cobalt, and the powerful 0.5-10h that stirs.
The process that said ball-shape nickel hydroxide with coated gamma-CoOOH carries out oxidation realizes through following steps: in 10% the NaOH aqueous solution of the ball-shape nickel hydroxide that is suspended with coated gamma-CoOOH, drip NaClO solution; And stir, regulate the average valence of nickel element in the compound through the consumption of control NaClO.
The preparation method's of this Ni-MH battery characteristics are may further comprise the steps:
1) anodal preparation; When preparing the positive electrode of battery; To coat one deck γ-CoOOH cover layer as the ball shape nickel hydroxide surface of positive active material earlier, the ball-shape nickel hydroxide with coated gamma-CoOOH carries out partial oxidation again, and the average valence of the nickel after the controlled oxidation is 2.15;
2) negative pole preparation; Negative pole is 1.25: 1.0 with anodal capacity ratio;
3) positive pole, negative pole and barrier film assembling;
4) battery changes into: adopt 0.05C-0.2C 3～10 weeks of activation, charge/discharge capacity weekly and is put the carried charge of battery to zero during first week discharge between 30%-100%.
With the prior art contrast, the beneficial effect that the present invention has is:
Battery positive electrode active material adopts the part of nickel oxidized surface to coat the ball-shape nickel hydroxide of γ-CoOOH; Regulate the negative discharge idle capacity; The average valence of nickel is chosen between the 2.08-2.20; When the average valence of selecting nickel when the nickel oxidation 2.08 below coats γ-CoOOH ball nickel manufacture batteries, the reduction deficiency of negative discharge idle capacity can not improve the cycle performance of battery effectively; When the average valence of selecting nickel when the nickel oxidation 2.20 or more coats γ-CoOOH ball nickel manufacture batteries, the charge volume minimizing of negative pole more causes battery changing into or overcharging leakage in the process.Preferably, through being adjusted in the amount of nickel oxidation between the 2.08-2.20 valence state, confirmed between the optimal zone of nickel valence state after the nickel oxidation between 2.14-2.16.
When positive pole adopts the ball-shape nickel hydroxide of the coated gamma-CoOOH of part of nickel oxidation, the capacity ratio one of both positive and negative polarity design has regularly reduced the available capacity proportioning of both positive and negative polarity, and the battery that adopts this technology to make can show the characteristic of long-life and overcharging resisting.The anodal ball nickel that adopts the coated gamma-CoOOH of part of nickel oxidation; The design capacity of negative pole can reduce accordingly, compares with common Ni-MH battery, under the prerequisite that does not reduce battery performance; Can reduce the consumption of negative electrode active material; Can reduce the last powder amount of negative pole, the conserve batteries cost of manufacture, and the cycle performance of battery is compared employing common ball nickel (the initial valence state of nickel is 2.0) Shi Buhui reduction; The initial valence state of nickel is 2.20 o'clock in the ball-shape nickel hydroxide of part of nickel oxidized surface coating γ-CoOOH, and the negative pole of design battery can reach to 1.1-1.25 with anodal capacity ratio (N/P).Or compare with common Ni-MH battery, do not change the consumption of negative electrode active material, can improve interior pressure performance, cycle performance and the overcharging resisting performance of battery.
When anode adopts the part of nickel oxidized surface to coat the ball-shape nickel hydroxide of γ-CoOOH; Adopt a kind of corresponding with it battery formation method; Be that battery has discharge step at the initial stage of changing into, when discharging for the first time, that battery discharge is extremely zero; Charging is reduced the 2.08-2.20 valency again after the oxidized rising of the average valence of nickel in the positive active material then.Help to obtain in the early stage complete expansion, the contraction of the volume of positive electrode like this, get through the diffusion of protons passage, help the gram volume performance of material, guaranteed that once the capacity of changing into reaches the rated capacity of design, can not cause the waste of battery gram volume.
Description of drawings
Fig. 1 is a Ni-MH battery both positive and negative polarity capacity distribution schematic diagram.
Embodiment
A kind of preparation method of Ni-MH battery may further comprise the steps:
1) preparation of positive pole.
Adopt ball-shape nickel hydroxide that the part of nickel oxidized surface coats γ-CoOOH as positive active material, and the initial average valence of control nickel is 2.08-2.20, its preparation method is following:
A) in the mixed solution of nickelous sulfate, zinc sulfate and cobaltous sulfate that brute force is stirring, dropwise add sodium hydrate aqueous solution; Through regulating pH value between 13～14; Make and separate out the ball-shape nickel hydroxide that is doped with zinc and cobalt in the solution uniformly, the mass ratio of metallic nickel, metallic zinc and metallic cobalt in the feasible ball-shape nickel hydroxide of separating out of controls reaction speed is 57: 3.0: 1.4.
B) in the solution of separating out nickel hydroxide, add 10%～25% the CoSO4 aqueous solution; The pH value that keeps reaction solution is between 9～10; Make nickel hydroxide surface wrap up the sub-compound of one deck cobalt uniformly; The shared proportion of controlling packet coating divides three times cleaning material in pure water in 5% of nickel hydroxide weight, and drying obtains powder body material.
C) in this powder body material, adding the sprinkle weight ratio is the NaOH solution of 30%～40% mass concentration of 5-8wt%, and the powerful 0.5-10h that stirs, and this process will be carried out in non-liquid system under 80-100 ℃ purity oxygen atmosphere.Fully detecting the surface coating material that obtains through XRD after the reaction is γ-CoOOH.
D) ball-shape nickel hydroxide with the above-mentioned coated gamma-CoOOH that obtains is a matrix, and the NaOH aqueous solution with this matrix and 10% is even by a certain percentage, is configured as the 10%NaOH suspension-turbid liquid of the ball-shape nickel hydroxide that is suspended with coated gamma-CoOOH.In this suspension-turbid liquid, dropwise splash into certain density NaClO solution, control the ball-shape nickel hydroxide of the pre-oxidation coated gamma-CoOOH that obtains the different oxidation numbers of pre-oxidation amount between 2.08-2.20 through the amount of splashing into of regulating NaClO solution.
The average valence of nickel is drawn by the average valence of nickel in the test anode of nickel-metal hydride battery discharging product in the positive discharge product.
The ball-shape nickel hydroxide that the part of nickel oxidized surface is coated γ-CoOOH is applied on the nickel foam as collector with dry method, and conduct is anodal after roll-in, the cut-parts.
2) preparation of negative pole: the design capacity ratio of both positive and negative polarity is 1: (1.15～1.25), the general commercial hydrogen-storage alloy powder is rolled in flakes with a kind of wire netting, immerse in the SBR glue, after oven dry under 120 ℃, cut into negative plate.
3) be barrier film with the PP/PE tunica fibrosa, with positive/negative plate and membrane coil around after, in the box hat of packing into, in box hat implantation quality percentage be 30% potassium hydroxide aqueous solution as electrolyte, then box hat being sealed the manufacturing capacity is the AA type battery of 1500mAh.
4) change into system: 0.05c-0.2c activation 3-10 week, wherein weekly charge/discharge capacity is between 30%-100%.Battery just is put into 0% with the carried charge of battery in first week of each week, the especially activation of activation.
Embodiment 1
According to the above method, the anodal initial valence state that adopts nickel is that the ball-shape nickel hydroxide of 2.15 part of nickel oxidation is as positive active material; By the both positive and negative polarity Capacity Ratio is to confirm powder amount N on the negative pole at 1.0: 1.25; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery A1.
Comparative example 1
The anodal general spherical shape nickel hydroxide that adopts is as active material; By the both positive and negative polarity Capacity Ratio is to confirm that the last powder amount of negative pole is N at 1.0: 1.25; Battery does not have discharge step in formation process, promptly before the complete activation of battery, do not comprise the step (chemical synthesis technology 2) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery A2.
The battery of embodiment 1 and comparative example 1 changes into the volume test result and sees table 1.Wherein, changing into discharge capacity calculates as 100 with the capacity of the battery A2 of comparative example 1.
Table 1
| Battery types | Anodal nickel valence state | Once change into capacity |
| A1 | 2.15 | 71.5 |
| A2 | 2.00 | 100 |
Can find out from the result of last table 1: after anodal employing general spherical shape nickel hydroxide carried out pre-oxidation treatment, the capacity of preparation battery was seriously influenced.The capacity that the Capacity Ratio common process that adopts common pre-oxidation ball nickel to prepare battery prepares battery descends 28.5%.
Embodiment 2
The anodal initial valence state that adopts nickel be 2.15 part of nickel oxidized surface coat γ-CoOOH ball-shape nickel hydroxide as positive active material; By the both positive and negative polarity Capacity Ratio is to confirm powder amount N on the negative pole at 1.0: 1.25; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery B1.Test that it overcharges, cycle performance and negative discharge deposit.
Ni-MH battery over-charging method of testing is: change into the back battery and put to 1.0V with the 0.2C multiplying power, the 1C 92min that charges requires battery not climb liquid, no leakage.
Ni-MH battery cycle performance method of testing: change into the back battery and carry out charge and discharge cycles with the multiplying power of 1C; The 1C discharge capacity of a certain circulation and the ratio of maximum discharge capacity are called the capability retention after a certain circulation of battery, and the battery capacity conservation rate is that 60% o'clock circulating cycle number is as the index of weighing cycle performance.
Negative discharge deposit method of testing: change into the back battery and be full of with the 0.2C multiplying power; Shelve 1h; Then with the strip off of battery seal place; Immerse with battery in soak 30min in the identical electrolyte that adopts, be 0V (vs.Hg/HgO) with battery with 0.2C multiplying power discharging to negative pole current potential, the time of writing down positive discharge to current potential and be 0V is t
Just, negative discharge to current potential is that the time of 0V is t
Negative, then the negative discharge deposit is (t
Negative-t
Just)/t
Just
Embodiment 3
The anodal initial valence state that adopts nickel be 2.06 part of nickel oxidized surface coat γ-CoOOH ball-shape nickel hydroxide as positive active material; By the both positive and negative polarity Capacity Ratio is to confirm powder amount N on the negative pole at 1.0: 1.25; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery B2.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
Embodiment 4
The anodal initial valence state that adopts nickel be 2.22 part of nickel oxidized surface coat γ-CoOOH ball-shape nickel hydroxide as positive active material; By the both positive and negative polarity Capacity Ratio is to confirm powder amount N on the negative pole at 1.0: 1.25; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery B3.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
Comparative example 2
The anodal general spherical shape nickel hydroxide (average valence of nickel is 2.0) that adopts is as active material; By the both positive and negative polarity Capacity Ratio is to confirm that the last powder amount of negative pole is N at 1.0: 1.25; Battery does not have discharge step in formation process, promptly before the complete activation of battery, do not comprise the step (chemical synthesis technology 2) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery B4.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
The battery of embodiment 2,3,4 and comparative example 2 changes into capacity, and the test result of over-charging, cycle performance and negative discharge deposit is seen table 2.Wherein, changing into discharge capacity calculates as 100 with the capacity of the battery B4 of comparative example 2.
Table 2
| Battery types | Anodal nickel valence state | Once change into capacity | Over-charging | The negative discharge deposit | Cycle performance |
| B1 | 2.15 | 100 | Do not have and climb liquid, leakage | 11％ | 700-720 week |
| B2 | 2.06 | 100 | Do not have and climb liquid, leakage | 22％ | 350-380 week |
| B3 | 2.22 | Change into leakage | / | / | ?/ |
| B4 | 2.00 | 100 | Do not have and climb liquid, leakage | 26％ | 350-380 week |
Can find out that from the result of last table 2 anodal nickel valence state is lower than 2.08, the negative discharge deposit is still very high, can not improve the cycle performance of battery effectively; And anodal nickel valence state is higher than 2.20, and capacity of negative plates has caused battery leakage in the formation process inadequately in the battery formation process.Therefore, the valence state of anodal nickel should be chosen between the 2.08-2.20.
Embodiment 5
The anodal initial valence state that adopts nickel be 2.08 part of nickel oxidized surface coat γ-CoOOH ball-shape nickel hydroxide as positive active material; By the both positive and negative polarity Capacity Ratio is to confirm powder amount N on the negative pole at 1.0: 1.25; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery C1.Test that it overcharges, cycle performance and negative discharge deposit.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
Embodiment 6
The anodal initial valence state that adopts nickel be 2.10 part of nickel oxidized surface coat γ-CoOOH ball-shape nickel hydroxide as positive active material; By the both positive and negative polarity Capacity Ratio is to confirm powder amount N on the negative pole at 1.0: 1.25; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery C2.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
Embodiment 7
The anodal initial valence state that adopts nickel be 2.12 part of nickel oxidized surface coat γ-CoOOH ball-shape nickel hydroxide as positive active material; By the both positive and negative polarity Capacity Ratio is to confirm powder amount N on the negative pole at 1.0: 1.25; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery C3.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
Embodiment 8
The anodal initial valence state that adopts nickel be 2.14 part of nickel oxidized surface coat γ-CoOOH ball-shape nickel hydroxide as positive active material; By the both positive and negative polarity Capacity Ratio is to confirm powder amount N on the negative pole at 1.0: 1.25; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery C4.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
Embodiment 9
The anodal initial valence state that adopts nickel be 2.16 part of nickel oxidized surface coat γ-CoOOH ball-shape nickel hydroxide as positive active material; By the both positive and negative polarity Capacity Ratio is to confirm powder amount N on the negative pole at 1.0: 1.25; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery C5.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
Embodiment 10
The anodal initial valence state that adopts nickel be 2.18 part of nickel oxidized surface coat γ-CoOOH ball-shape nickel hydroxide as positive active material; By the both positive and negative polarity Capacity Ratio is to confirm powder amount N on the negative pole at 1.0: 1.25; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery C6.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
Embodiment 11
The anodal initial valence state that adopts nickel be 2.20 part of nickel oxidized surface coat γ-CoOOH ball-shape nickel hydroxide as positive active material; By the both positive and negative polarity Capacity Ratio is to confirm powder amount N on the negative pole at 1.0: 1.25; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery C7.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
The battery of embodiment 5～11 changes into the test result of capacity, over-charging, cycle performance and negative discharge deposit and sees table 3.Wherein, changing into discharge capacity calculates as 100 with the capacity of the battery C1 of embodiment 5.
Table 3
| Battery types | Anodal nickel valence state | Once change into capacity | Over-charging | The negative discharge deposit | Cycle performance |
| C1 | 2.08 | 100 | Do not have and climb liquid, leakage | 18％ | 400-430 week |
| C2 | 2.10 | 100 | Do not have and climb liquid, leakage | 16％ | 500-530 week |
| C3 | 2.12 | 100 | Do not have and climb liquid, leakage | 14％ | 600-630 week |
| C4 | 2.14 | 100 | Do not have and climb liquid, leakage | 12％ | 680-710 week |
| C5 | 2.16 | 100 | Do not have and climb liquid, leakage | 10％ | 700-730 week |
| C6 | 2.18 | 100 | Climb liquid, leakage | 8％ | 720-740 week |
| C7 | 2.20 | 100 | Climb liquid, leakage | 6％ | 730-750 week |
Can find out that from the result of table 3 anodal nickel valence state raises constantly between 2.08-2.14 and gradually, the negative discharge deposit reduces gradually, and the cycle performance of battery increases rapidly.When anodal nickel valence state between 2.14-2.16 and when raising gradually, the negative discharge deposit reduces gradually, and the cycle performance of battery changes and tends towards stability, and changes little.When anodal nickel valence state also raise between 2.16-2.20 gradually, the negative discharge deposit reduced gradually, and the cycle performance of battery changes mild, but the over-charging of battery descends.When therefore, the valence state of positive pole is between 2.14-2.16 is between the optimal zone of nickel valence state.
Embodiment 12
With reference to the test result of table 1, table 2 and table 3, the anodal initial valence state that adopts nickel be 2.15 part of nickel oxidized surface coat γ-CoOOH ball-shape nickel hydroxide as positive active material; By the both positive and negative polarity Capacity Ratio is to confirm powder amount N on the negative pole at 1.0: 1.25; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery D1.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
Comparative example 3
With reference to the test result of table 1, table 2 and table 3, the anodal initial valence state that adopts nickel is that 2.15 part of nickel oxidized surface coats γ-CoOOH ball-shape nickel hydroxide as positive active material; By the both positive and negative polarity Capacity Ratio is to confirm powder amount N on the negative pole at 1.0: 1.25; Battery not with the step of discharge of electricity to 0%, promptly before the complete activation of battery, does not comprise the step (chemical synthesis technology 2) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again in formation process.Battery with this manufacture craft and chemical synthesis technology preparation is battery D2.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
Embodiment 12 changes into capacity with the battery of comparative example 3, and the test result of over-charging, cycle performance and negative discharge deposit is seen table 4.Wherein, changing into discharge capacity calculates as 100 with the capacity of the battery D1 of embodiment 12.
Table 4
| Battery types | Chemical synthesis technology | Once change into capacity | Over-charging | The negative discharge deposit | Cycle performance |
| D1 | Chemical synthesis technology 1 | 100 | Do not have and climb liquid, leakage | 11％ | 700-720 week |
| D2 | Chemical synthesis technology 2 | 90 | Do not have and climb liquid, leakage | 11％ | 700-720 week |
Can find out from the result of table 4; The chemical synthesizing method that the present invention proposes has guaranteed the higher capacity that once changes into, and this is because comprised the step that is reduced the 2.08-2.20 valency after the average valence of nickel raises in the positive active material again in the chemical synthesis technology of proposition of the present invention.
Embodiment 14
With reference to the test result of table 1, table 2 and table 3, the anodal initial valence state that adopts nickel be 2.15 part of nickel oxidized surface coat γ-CoOOH ball-shape nickel hydroxide as positive active material; By both positive and negative polarity Capacity Ratio (N/P value) is to confirm powder amount on the negative pole at 1.0: 1.25; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery E1.Test that it overcharges, cycle performance and negative discharge deposit.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
Embodiment 15
With reference to the test result of table 1, table 2 and table 3, the anodal initial valence state that adopts nickel be 2.15 part of nickel oxidized surface coat γ-CoOOH ball-shape nickel hydroxide as positive active material; The N/P value is 1.20 through adjustment negative pole powder amount design N/P value promptly than reducing 0.05 among the embodiment 14; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery E2.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
Embodiment 16
With reference to the test result of table 1, table 2 and table 3, the anodal initial valence state that adopts nickel be 2.15 part of nickel oxidized surface coat γ-CoOOH ball-shape nickel hydroxide as positive active material; The N/P value is 1.15 through adjustment negative pole powder amount design N/P value promptly than reducing 0.05 among the embodiment 15; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery E3.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
Embodiment 17
With reference to the test result of table 1, table 2 and table 3, the anodal initial valence state that adopts nickel be 2.15 part of nickel oxidized surface coat γ-CoOOH ball-shape nickel hydroxide as positive active material; The N/P value is 1.10 through adjustment negative pole powder amount design N/P value promptly than reducing 0.05 among the embodiment 16; Battery has discharge step in formation process, promptly before the complete activation of battery, comprise the step (chemical synthesis technology 1) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery E4.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
Comparative example 4
The anodal general spherical shape nickel hydroxide that adopts is as active material, and the average valence of nickel is 2.0; By the both positive and negative polarity Capacity Ratio is the last powder amount of 1.0: 1.25 definite negative poles; Battery does not have discharge step in formation process, promptly before the complete activation of battery, do not comprise the step (chemical synthesis technology 2) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery E5.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
Comparative example 5
The anodal general spherical shape nickel hydroxide that adopts is as active material, and the average valence of nickel is 2.0; The N/P value is 1.20 through adjustment negative pole powder amount design N/P value promptly than reducing 0.05 in the comparative example 4; Battery does not have discharge step in formation process, promptly before the complete activation of battery, do not comprise the step (chemical synthesis technology 2) that is reduced the 2.08-2.20 valency in the positive active material after the oxidized rising of the average valence of nickel again.Battery with this manufacture craft and chemical synthesis technology preparation is battery E6.Overcharge, the method for testing of cycle performance and negative discharge deposit is with embodiment 2.
The battery of embodiment 14-17 and comparative example 4,5 changes into capacity, and the test result of over-charging, cycle performance and negative discharge deposit is seen table 5.Wherein, changing into discharge capacity calculates as 100 with the capacity of the battery E1 of embodiment 14.
Table 5
Can find out from the result of above-mentioned table 6; When the ball-shape nickel hydroxide that adopts the part of nickel oxidized surface to coat γ-CoOOH was made positive pole, the reduction of the N/P value of design battery had certain influence to the cycle performance of battery, after exceeding certain limit; Capacity of negative plates is not enough, has caused the over-charging variation.Can not be affected at the capacity of 1.15-1.25 battery when designing the N/P value, and the reduction of circulation can not be lower than the cycle-index of common process manufacture batteries.Therefore the ball-shape nickel hydroxide that coats γ-CoOOH when anodal employing part of nickel oxidized surface is made; Can reduce the consumption of negative pole accordingly; Adjustment design N/P value can reduce the negative pole consumption, reduce the cycle performance that does not influence battery under the design battery material condition of cost between 1.15-1.25.
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, can also make some simple deduction or replace, all should be regarded as belonging to protection scope of the present invention.
Claims (1)
1. the preparation method of a Ni-MH battery is characterized in that may further comprise the steps:
1) anodal preparation; When preparing the positive electrode of battery; To coat one deck γ-CoOOH cover layer as the ball shape nickel hydroxide surface of positive active material earlier, the ball-shape nickel hydroxide with coated gamma-CoOOH carries out partial oxidation again, and the average valence of the nickel after the controlled oxidation is 2.15;
2) negative pole preparation; Negative pole is 1.25: 1.0 with anodal capacity ratio;
3) positive pole, negative pole and barrier film assembling;
4) battery changes into: adopt 0.05C-0.2C 3～10 weeks of activation, charge/discharge capacity weekly and is put the carried charge of battery to zero during first week discharge between 30%-100%.
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| US8048566B2 (en) * | 2008-02-07 | 2011-11-01 | Powergenix Systems, Inc. | Nickel hydroxide electrode for rechargeable batteries |
| CN101908612B (en) * | 2010-08-10 | 2012-08-29 | 珠海市光环自动化科技有限公司 | Automatic powdering box for anode of secondary battery |
| JP5213989B2 (en) * | 2011-04-27 | 2013-06-19 | 住友金属鉱山株式会社 | Coated nickel hydroxide powder for positive electrode active material of alkaline secondary battery and method for producing the same |
| CN104995782A (en) | 2013-01-14 | 2015-10-21 | 鲍尔热尼系统公司 | Pasted nickel hydroxide electrode and additives for rechargeable alkaline batteries |
| JP7348220B2 (en) * | 2021-02-25 | 2023-09-20 | プライムアースＥｖエナジー株式会社 | Manufacturing method of nickel metal hydride storage battery |
| CN114142096A (en) * | 2021-10-20 | 2022-03-04 | 合肥国轩高科动力能源有限公司 | Method for reducing low SOC impedance of lithium ion battery |
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