CN101162787A - Method for improving shelf characteristic of nickel-hydrogen battery - Google Patents
Method for improving shelf characteristic of nickel-hydrogen battery Download PDFInfo
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- CN101162787A CN101162787A CNA2007100467042A CN200710046704A CN101162787A CN 101162787 A CN101162787 A CN 101162787A CN A2007100467042 A CNA2007100467042 A CN A2007100467042A CN 200710046704 A CN200710046704 A CN 200710046704A CN 101162787 A CN101162787 A CN 101162787A
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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
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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
- 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
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Abstract
The present invention relates to a method for improving the storage performance of a nickel hydrogen battery, which is characterized in that: the storage performance of the nickel hydrogen battery is improved by increasing the stability of anode cobalt compound conductive network on the premise of no impact on the initial capacity of the battery, thereby reducing the capacity attenuation of the nickel hydrogen battery after long time storage. The method is characterized in that the anode formulation is adjusted: reducing the content of additive CoO, replacing the reduction with addition of other conductive material such as single substance metal Co power or Co(OH)2, wherein the addition quantity of which is from 1wt percent to 9wt percent and the addition quantity of CoO is changed from 4wt percent to 10wt percent to 0wt percent to 3wt percent. One or more calcium compound of 0.5 wt percent to 10wt percent is added into the anode formulation, wherein the calcium compound mainly includes: one or several among Ca(OH)2, Ca(OH)2 and CaF2, CaCO3 or CaCl2.
Description
Technical Field
The invention relates to a preparation method of a nickel-metal hydride battery with high storage performance, in particular to a method capable of inhibiting the storage capacity of the nickel-metal hydride battery from being attenuated under the conditions of high temperature and long time, belonging to the technical field of energy.
Background
The positive electrode of a metal hydride nickel battery (nickel-hydrogen battery for short) is generally prepared by a paste coating method or a dry method by using a foam nickel matrix, and cobaltous oxide (CoO) is generally added into the positive electrode as a conductive agent.
The nickel-hydrogen battery is usually precharged with a certain electric quantity before leaving a factory, then a hanging box is used for blister packaging, and finally the nickel-hydrogen battery reaches the hands of consumers through storage, transportation and distribution, at least 2 months are needed, and the time of the product being completely sold out is difficult to estimate, so that the problem of long-term storage of the battery exists. The battery may also be left unused for a long period of time during use by the user. In addition, the environment for packaging, transportation and storage is always at a high temperature of more than 30 ℃, and the temperature in the container can reach 50-60 ℃ during sea transportation. In this case, the open circuit voltage of some batteries is lowerthan 1.0V in about 3 months after the original battery is shipped with 50% of charge, and the batteries cannot be recharged without removing the external package, so that as time goes on, a series of problems such as about 20% of capacity reduction, internal resistance increase and charging voltage increase occur when the batteries are recharged.
It has been proposed to deliver batteries after they have been fully charged to alleviate the above-mentioned adverse symptoms, but delivery of batteries in a fully charged state may result in an accident in which the individual batteries are short-circuited during transportation to cause fire in the entire battery pack. Similar accidents occur in China, so that the fire is caused, and the factory can only leave in a partial charging state. Some documents (V.Pralong, A.Delahayeye-Vidal, B.Beaudion, et al.Bismuth-enhanced chemical stability of cobalt used as an additive in Ni/Cd and Ni/metal hydride batteries. J.electrochemical society.2000 (147): 2096-It is proposed to add Bi to the positive electrode2O3With Bi2O3Increase of the added amount, and rate of decay of capacity of the nickel-hydrogen battery after storageGradually decreases but with Bi2O3The addition of Bi to the positive electrode reduces the initial capacity of the battery by 5 to 20 percent as well due to the increase of the addition amount2O3The method for improving the storage performance of the nickel-metal hydride battery is at the cost of reducing the initial capacity of the battery. Some have used over-capacity design methods to bring the actual capacity of the battery to 110% or more of the nominal capacity in order to compensate for capacity fade due to storage; patent (02135009.4) also proposes to use a conductive agent such as graphite, acetylene black, nickel carbonyl powder, etc. instead of the main conductive agent cobalt protoxide in a nickel-hydrogen battery, but this does not fundamentally solve the problem, and the battery requires a lot of raw materials and lowers the specific characteristics.
The current research finds that: nickel-metal hydride batteries are known to undergo the following transformations during the shelf life of the closure and during initial charging:
that is, CoO is first dissolved in the electrolyte to form Co2+Complex, then converted to β -Co (OH)2And redeposit on Ni (OH)2Particle surface in initial charging process, β -Co (OH)2Oxidized and uniformly distributed in the form of β -CoOOH, the conductivity of the CoOOH is 12.8S/cm, which is much larger than that of NiOOH by 0.15S/cm, as a very effective conductive network, the CoOOH greatly improves Ni (OH)2Utilization of (2), in particular of Ni (OH) based on foamed nickel2And (4) a positive electrode.
During the storage of the nickel-metal hydride battery, CoOOH is firstly replaced by H2Reduction to Co (OH)2The latter, with unreduced CoOOH, forms inert Co3O4Resulting in the destruction of the positive CoOOH conductive network, which in turn causes irreversible degradation of the cell performance.
The invention aims to improve the storage performance of the nickel-metal hydride battery by improving the stability of the positive electrode conductive network on the premise of not influencing the initial capacity of the battery and reduce the capacity fading of the nickel-metal hydride battery after long-time storage.
Disclosure of Invention
The invention aims to provide a method for improving the storage performance of metal hydride, namely a preparation method of a metal hydride nickel battery with high storage performance.
The core technology of the invention is to provide a new positive electrode composition for manufacturing a nickel-metal hydride battery, thereby achieving the purpose of the invention.
The invention is characterized in that the storage performance of the nickel-hydrogen battery is improved by improving the stability of the positive electrode network on the premise of not influencing the initial capacity of the battery, wherein the improvement of the stability of the positive electrode network is realized by reducing the content of a conductive agent CoO in the positive electrode composition by ① and adding other conductive agents instead of the conductive agent CoO, ② adding calcium additives, ③ adjusting the composition of active substances to form an adjusted positive electrode composition.
The existing widely used anode formula is as follows: the conductive material comprises nickel hydroxide serving as an active material, a CoO conductive agent accounting for 4-10 wt% (based on the weight of the nickel hydroxide, the same applies below) and a small amount of a binder.
The anode formula provided by the invention is as follows: the content of additive CoO is reduced, and other conductive agents, such as elementary metal Co powder or Co (OH), are added instead2The addition amount is 1-9 wt%, and the addition amount of CoO is adjusted to 0-3 wt% from the original 4-10 wt%. Adding 0.5-10 wt% of one or more calcium compounds into the positive electrode formula, wherein the calcium compounds mainly comprise: ca (OH)2(calcium hydroxide), CaF2(calcium fluoride), CaCO3(calcium carbonate) and CaCl2(calcium chloride), and the like. The positive electrode and the negative electrode of the battery both adopt the manufacturing process of a normal electrode, namely, the positive electrode and the negative electrode are both composed of a conductive framework, an active substance, a proper conductive agent and a proper adhesive. The skeleton is made of foamed nickel, cut and drawn net, nickel-plated steel band and woven net, and the electrodes are made by paste-coating, dry and sintering processes. In the positive electrode formula:
1. active substance: adding nickel hydroxide of various types and/or cobalt (the coating amount of cobalt is 1-10 wt%) coated nickel hydroxide of one or more of zinc (0-6 wt%), cadmium (0-6 wt%) and cobalt (0-6 wt%); the mass percentage is based on nickel hydroxide (the same below).
2. Conductive agent: elemental metal Co powder, Co (OH)2And/or CoO, wherein the mass percent of the CoO is 0-3%, and the metal simple substance Co or Co (OH)2The mass percentage of the component (A) is 1-9 wt%.
3. Calcium-based additive: ca (OH)2、CaF2、CaCO3Or CaCl2，Ca(OH)2Is added, namely the calcium additive is single Ca (OH)2Or is Ca (OH)2And CaF2、CaCO3、CaCl2One or more calcium additives are added in an amount of 0.5-10 wt% of the nickel hydroxide;
4. a small amount of at least one of CMC (sodium carboxymethylcellulose), HPMC (hydroxypropyl methylcellulose), PTFE (polytetrafluoroethylene), SBR (styrene butadiene rubber) and other adhesives, and the total addition amount is 0.1-5 wt% of nickel hydroxide.
The basic invention points of the invention are that:
1. reducing the CoO content in the positive electrode formula by adopting metal Co powder or Co (OH)2The stability of the CoOOH conductive network can be effectively improved, and the storage performance of the MH/Ni battery is further improved.
2、Ca(OH)2CaF and CaCl include Ca (OH)2The one or more calcium additives in the nickel-metal hydride battery can improve the high-temperature charging efficiency of the nickel-metal hydride battery, improve the initial capacity of the battery by 1-3%, and simultaneously ensure the stability of a CoOOH conductive network when the battery is stored at a higher temperature. The application of the method ensures that the capacity fading rate of the nickel-hydrogen battery after one year of storage is less than 5 percent.
Detailed Description
Example 1: cylinder type with 8000 mm capacity (33.5 mm diameter)-0.5mm, height 60.5-1.0mm) nickel-metal hydride battery was prepared as follows: the surface density of the positive electrode framework is 300-500g/m2The active substance adopts cobalt-coated zinc-added oxyhydrogenNickel sulfide, other additives: 4 wt% elemental metal Co powder, 1.5 wt% Ca (OH)20.4 wt% HPMC, 0.8 wt% PTFE, 45g of weight of positive plate made, size 520 x 46.5 x 0.58 mm; the negative electrode adopts a nickel-plated steel strip with the surface density of 150-300, adopts lanthanum-rich alloy powder with the granularity of 180-250 meshes, and comprises the following additives: 1 wt% nickel powder, 2 wt% SBR, 1.5 wt% CMC, negative plate weight 57g, size 600 x 47 x 0.33 mm. The specific gravity of the electrolyte is 1.3g/cm3The KOH electrolyte contains 20g/l of LiOH, a polypropylene diaphragm with the thickness of 0.14mm is adopted, the 0.2C capacity of the manufactured battery is 8256mAh, the 0.2C capacity is 8173mAh after the KOH electrolyte is placed at the normal temperature for 1 year ina discharge state, and the capacity fading rate is only 1.0 percent. The mass percentage is based on nickel hydroxide (the same as below).
Example 2: cylindrical shape (diameter of 10.2) with capacity of 600-0.2mm, height 43.0-1.0mm) nickel-metal hydride battery was prepared as follows: the surface density of the positive electrode framework is 300-500g/m2The active substance of the foamed nickel adopts zinc-added nickel hydroxide, and other additives are as follows: 4 wt% elemental metal Co powder, 1.5 wt% Ca (OH)20.4 wt% HPMC, 0.8 wt% PTFE, 3.2g of weight of the fabricated positive plate, size 45 x 35 x 0.59 mm; the negative electrode adopts a nickel-plated steel strip with the surface density of 150-300, adopts lanthanum-rich alloy powder with the granularity of 180-250 meshes, and comprises the following additives: 1 wt% nickel powder, 2 wt% SBR, 1.5 wt% CMC, manufactured positive plate weight 4.0g, size 67 x 35 x 0.27 mm; the rest of the process parameters were the same as in example 1The 0.2C capacity of the battery is 656mAh, 0.2C capacity of 625mAh is 0.2C capacity after the battery is placed at normal temperature for 1 year in a discharge state, and the capacity fading rate is 4.7 percent.
Example 3: cylindrical shape (diameter of 14.5) with capacity of 1800-0.5mm, height 50-1mm) nickel-metal hydride battery was prepared as follows: the surface density of the positive electrode framework is 300-500g/m2The active substance of the foamed nickel adopts zinc-added nickel hydroxide, and other additives are as follows: 3 wt% elemental metal Co powder, 2 wt% CoO, 0.5 wt% Ca (OH)20.5 wt% of CaF20.4 wt% HPMC, 0.8 wt% PTFE, manufactured positive plate weight 9.0g, size 94 x 42.5 x 0.65 mm; the negative electrode has the surface density of 150-300The nickel-plated steel strip is prepared from cerium-rich alloy powder withthe granularity of 180-250 meshes and additives: 1 wt% nickel powder, 2 wt% SBR, 1.5 wt% CMC, the weight of the manufactured positive plate was 10.0g, the size was 132 × 42.5 × 0.28 mm; the other process parameters are the same as the example 1, the manufactured battery has the capacity of 0.2C of 1860mAh, the capacity of 0.2C of 1795mAh after the battery is placed at the discharge state for 1 year at normal temperature, and the capacity fading rate is 3.5 percent.
Comparative examples 1 to 3: in the range specified by the invention, although the types and capacities of the batteries are different, and the positive electrode formulas are slightly different, the capacity fading rate of the batteries after storage is reduced to be within 5 percent, which shows that the method has wider application range on the metal hydride nickel batteries.
Claims (7)
1. A method for improving the storage performance of a nickel-metal hydride battery is characterized in that the storage performance of the nickel-metal hydride battery is improved by improving the stability of a positive electrode network on the premise of not influencing the initial capacity of the battery, wherein the improvement of the stability of the positive electrode network is implemented by reducing the content of a conductive agent CoO in the positive electrode composition by ①, replacing the conductive agent with other conductive agents, adding ② calcium additives and adjusting the composition of active substances by ③ so as to construct an adjusted positive electrode composition.
2. The method for improving the storage performance of a nickel-metal hydride battery as claimed in claim 1, wherein the composition of the positive electrode after adjustment is as follows:
① the active substance is nickel hydroxide added with one or more of Zn, Cd and Co and/or nickel hydroxide coated with Co, the mass percentage of the added Zn, Cd or Co is 0-6%, and the mass percentage of the coated Co is 1-10%;
② the conductive agent is CoO, Co (OH) as metal simple substance2And/or CoO, wherein the mass percent of the CoO is 0-3%, and the metal simple substance Co or Co (OH)2The mass percentage content of the components is 1-9 wt%;
③ the calcium additive is Ca (OH)2Or Ca (OH)2And CaF2、CaCO3、CaCl2One or more of the components0.5-10% of calcium additive by mass percent;
④ the adhesive is at least one of sodium hydroxymethyl cellulose, hydroxypropyl methylcellulose, polytetrafluoroethylene and styrene butadiene rubber, and the added mass percentage is 0.1-5%;
the mass percentage content is based on nickel hydroxide.
3. The method for improving the storage performance of a nickel-metal hydride battery as claimed in claim 1, wherein the positive electrode has a skeleton made of foamed nickel, cut and drawn mesh, nickel-plated steel strip or woven mesh.
4. The method as set forth in claim 3, wherein the foamed nickel has an areal density of 300-500g/m2。
5. A method for improving the storage performance of a nickel-metal hydride battery as claimed in claim 2 or 3, wherein the positive electrode skeleton is foamed nickel, and the adjusted positive electrode composition is:
① the active substance is nickel hydroxide coated with Co and added with zinc;
② the conductive agent is simple substance Co with the mass percentage of 4%;
③ the calcium supplement is Ca (OH) with a mass percentage of 1.5%2；
④ the adhesive is hydroxypropyl methylcellulose 0.4 wt% and polytetrafluoroethylene 0.8 wt%;
the mass percentage is based on nickel hydroxide.
6. A method for improving the storage performance of a nickel-metal hydride battery as claimed in claim 2 or 3, wherein the positive electrode skeleton is foamed nickel, and the composition of the adjusted positive electrode is as follows:
① the active substance is nickel hydroxide added with Zn;
② elemental metal Co with the conductive agent mass percentage of 4%;
③ the calcium supplement is Ca (OH) with a mass percentage of 1.5%2；
④ the adhesive is hydroxypropyl methylcellulose 0.4 wt% and polytetrafluoroethylene 0.8 wt%;
the mass percentage is based on nickel hydroxide.
7. A method for improving the storage performance of a nickel-metal hydride battery as claimed in claim 2 or 3, wherein the positive electrode skeleton is made of foamed nickel, and the adjusted positive electrode composition is as follows:
① the active substance is nickel hydroxide coated with Co and added with zinc;
② the conductive agent is elementary Co with the mass percentage of 3% and CoO with the mass percentage of 2%;
③ the calcium supplement is 0.5 wt% Ca (OH)2And 0.5 percent of CaF by mass2；
④ the adhesive is hydroxypropyl methylcellulose or polytetrafluoroethylene with the mass percentage of 0.4 percent and 0.8 percent respectively;
the mass percentage is based on nickel hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100467042A CN101162787A (en) | 2007-09-29 | 2007-09-29 | Method for improving shelf characteristic of nickel-hydrogen battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100467042A CN101162787A (en) | 2007-09-29 | 2007-09-29 | Method for improving shelf characteristic of nickel-hydrogen battery |
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| CN101162787A true CN101162787A (en) | 2008-04-16 |
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| CNA2007100467042A Pending CN101162787A (en) | 2007-09-29 | 2007-09-29 | Method for improving shelf characteristic of nickel-hydrogen battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593435A (en) * | 2012-02-24 | 2012-07-18 | 深圳市力可兴电池有限公司 | Nickel-hydrogen battery capable of being used in low-temperature environment and preparation method thereof |
| CN102760874A (en) * | 2011-04-28 | 2012-10-31 | 比亚迪股份有限公司 | Nickel battery positive active material and preparation method thereof and nickel-metal hydride battery |
-
2007
- 2007-09-29 CN CNA2007100467042A patent/CN101162787A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760874A (en) * | 2011-04-28 | 2012-10-31 | 比亚迪股份有限公司 | Nickel battery positive active material and preparation method thereof and nickel-metal hydride battery |
| CN102760874B (en) * | 2011-04-28 | 2015-03-04 | 比亚迪股份有限公司 | Nickel battery positive active material and preparation method thereof and nickel-metal hydride battery |
| CN102593435A (en) * | 2012-02-24 | 2012-07-18 | 深圳市力可兴电池有限公司 | Nickel-hydrogen battery capable of being used in low-temperature environment and preparation method thereof |
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