CN108155382A - A kind of positive electrode of Ni-MH battery - Google Patents

A kind of positive electrode of Ni-MH battery Download PDF

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Publication number
CN108155382A
CN108155382A CN201711203064.1A CN201711203064A CN108155382A CN 108155382 A CN108155382 A CN 108155382A CN 201711203064 A CN201711203064 A CN 201711203064A CN 108155382 A CN108155382 A CN 108155382A
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CN
China
Prior art keywords
positive electrode
additive
cobalt
battery
conductive agent
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
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CN201711203064.1A
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Chinese (zh)
Inventor
邓荣
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Dongguan City Feng New Energy Science And Technology Ltd Co
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Dongguan City Feng New Energy Science And Technology Ltd Co
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Priority to CN201711203064.1A priority Critical patent/CN108155382A/en
Publication of CN108155382A publication Critical patent/CN108155382A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides a kind of positive electrodes of Ni-MH battery, including positive electrode, the positive electrode includes active material, conductive agent, adhesive, additive, the conductive agent is cobalt powder, one kind in cobalt oxide, cobalt protoxide, and the additive is titanium oxide, the composition of calcirm-fluoride, praseodymium neodymium oxides.Present invention aims at past Ni (OH)2Cobalt is added in electrode, in activation stage charging process, the CoOOH of high conductivity is oxidized to, its electron conduction and capacitance can be increased；Additive is titanium oxide, the composition of calcirm-fluoride, praseodymium neodymium oxides, ensure that the potential stability of battery.

Description

A kind of positive electrode of Ni-MH battery
Technical field
The present invention relates to Ni-MH battery fields, and in particular to a kind of positive electrode of Ni-MH battery.
Background technology
Ni-MH battery is synthesized by hydrogen ion and metallic nickel, and Power Reserve is than Ni-Cr battery higher, weight ratio Ni-Cr battery Gently, service life is long, and memory-less effect, environmentally safe since Ni-MH battery is without cadmium element.Therefore, ni-mh electricity Pond is widely used in today's society as a kind of environmentally protective rechargeable battery.The shortcomings that Ni-MH battery is price ratio Nickel-cadmium cell is expensive, and performance ratio lithium battery wants poor, Ni-MH battery memory-less effect.Anode of nickel-metal hydride battery active material is hydroxide Nickel, negative electrode active material are metal oxide, also referred to as hydrogen-storage alloy, and electrolyte is potassium hydroxide.During charging, hydrogen is precipitated in cathode Gas, in a reservoir, anode becomes nickel hydroxide (NiOOH) and H2O by hickelous nydroxide for storage；Hydrogen quilt on cathode during electric discharge It consumes, anode becomes hickelous nydroxide by nickel hydroxide.
At Ni (OH)2Cobalt is added in electrode, in activation stage charging process, is oxidized to the CoOOH of high conductivity, energy Increase its electron conduction and capacitance, improve the utilization rate of positive active material, so as to improve the electric conductivity of pole piece, improve Charge-discharge performance and increase overpotential for oxygen evolution.But cobalt compound can improve positive and negative anodes potential difference also reduce simultaneously it is positive and negative The stability of pole reaction, therefore, it is necessary to increase a kind of additive, makes Ni (OH)2Electrode can guarantee when electric conductivity is increased The stability of electrode.
The Chinese invention patent of Publication No. CN104157865A《A kind of nickel-hydrogen battery positive pole material》Disclose a kind of nickel The positive electrode of hydrogen battery adds in the compositions such as molybdenum trioxide, cobalt protoxide, so as to improve nickel electroactive material in additive Still, the additive level in the invention is 0.1-1wt% by utilization rate, the discharge potential for improving nickel electrode and service life, and The content of adhesive is but up to 6-10% so that and battery discharge effect is not significantly improved, and the ratio of adhesive is too high, Affect the discharge performance of positive and negative anodes.
On the other hand, due in anode cobalt compound be dissolved in concentrated base and form cobalt complex, will after it moves to diaphragm Diaphragm molecular oxidation itself is reduced into cobalt and is deposited on diaphragm, while cobalt complex also reaches negative plate through diaphragm, when Cathode is reduced into cobalt and deposits when charging.The cobalt being deposited on diaphragm can penetrate barrier film shape after running up to certain amount Into very thin " cobalt bridge ", electronic conduction occurs, initially causes micro-short circuit, develops into dead short later, so as to make battery failure, Even if the cobalt being deposited on cathode does not generate " cobalt bridge ", it is also possible to since the cobalt that negative terminal surface is grown up in tip is sent out in charge and discharge It gives birth to point discharge and leads to micro-short circuit.Therefore, it in order to avoid the generation of this micro-short circuit, needs to add in positive electrode Substance, make cobalt compound in charge and discharge process favorable dispersibility without being enriched on diaphragm.
Invention content
In view of the above problems, the present invention provides a kind of positive electrode of Ni-MH battery, conductive agent is cobalt powder, cobalt oxide, oxygen Change one kind in sub- cobalt, at Ni (OH)2Cobalt is added in electrode, in activation stage charging process, is oxidized to high conductivity CoOOH can increase its electron conduction and capacitance；Additive is titanium oxide, the composition of calcirm-fluoride, praseodymium neodymium oxides, is protected The potential stability of battery is demonstrate,proved.
To achieve the above object, the present invention solves by the following technical programs：
A kind of positive electrode of Ni-MH battery, including positive electrode, the positive electrode include active material, conductive agent, Adhesive, additive, the conductive agent is cobalt powder, one kind in cobalt oxide, cobalt protoxide, and the additive is titanium oxide, fluorine Change the composition of calcium, praseodymium neodymium oxides.
Specifically, the content of the conductive agent is 2~10wt% of positive electrode total amount.
Specifically, the average grain diameter of the conductive agent powder is 0.5~15 μm.
Specifically, the content of the additive is 1~3wt% of positive electrode total amount.
Specifically, each component ratio of the additive is：Titanium oxide：Calcirm-fluoride：Praseodymium neodymium oxides=20~25:45~ 60:15~20.
Specifically, the active material is hickelous nydroxide.
Specifically, mixture of the described adhesive for polytetrafluoroethylene (PTFE) and butadiene-styrene rubber composition.
The beneficial effects of the invention are as follows：
First, conductive agent is cobalt powder, one kind in cobalt oxide, cobalt protoxide, in charging process, is oxidized to high conductivity CoOOH, its electron conduction and capacitance can be increased, improve the utilization rate of positive active material, so as to improve pole piece Electric conductivity improves charge-discharge performance and increase overpotential for oxygen evolution, so as to reduce charging voltage, improve charge efficiency.
Second, the content of conductive agent is 2~10wt% of positive electrode total amount, and the compound of the content range cobalt is shown Best electrical conductive activities, electron conduction are best.
Third, titanium oxide is added in additive, and titanium oxide makes the dispersibility of conductive agent more preferable.
4th, calcirm-fluoride, the good fluidity of calcirm-fluoride, convenient for the cohesion and separation of metal, so as to make are added in additive Electrode reaction process it is steady.
5th, add in praseodymium neodymium oxides in additive, praseodymium neodymium oxides can during cell reaction in adhesive Polytetrafluoroethylene (PTFE) combines, hence it is evident that enhances the wearability of positive electrode.
Description of the drawings
Fig. 1 is the embodiment of the present invention one and the discharge curve of comparative example two.
Specific embodiment
In order to further appreciate that the feature of the present invention, technological means and the specific purposes reached, function, tie below Closing specific embodiment, the present invention is described in further detail.
Embodiment one：
As shown in Figure 1.
A kind of positive electrode of Ni-MH battery, including positive electrode, positive electrode includes active material, conductive agent, bonding Agent, additive.
Preferably, active material is hickelous nydroxide.
Preferably, mixture of the adhesive for polytetrafluoroethylene (PTFE) and butadiene-styrene rubber composition.
Preferably, conductive agent is the cobalt powder that average grain diameter is 0.5~15 μm.
Preferably, the content of cobalt powder is the 2wt% of positive electrode total amount.
Preferably, the content of additive is 1~3wt% of positive electrode total amount.
Preferably, additive is that each component ratio is：Titanium oxide：Calcirm-fluoride：Praseodymium neodymium oxides=20~25:45~60: 15~20.
Embodiment two：
A kind of positive electrode of Ni-MH battery, including positive electrode, positive electrode includes active material, conductive agent, bonding Agent, additive.
Preferably, active material is hickelous nydroxide.
Preferably, mixture of the adhesive for polytetrafluoroethylene (PTFE) and butadiene-styrene rubber composition.
Preferably, conductive agent is the cobalt powder that average grain diameter is 0.5~15 μm.
Preferably, the content of cobalt powder is the 4wt% of positive electrode total amount.
Preferably, the content of additive is 1~3wt% of positive electrode total amount.
Preferably, additive is that each component ratio is：Titanium oxide：Calcirm-fluoride：Praseodymium neodymium oxides=20~25:45~60: 15~20.
Embodiment three：
A kind of positive electrode of Ni-MH battery, including positive electrode, positive electrode includes active material, conductive agent, bonding Agent, additive.
Preferably, active material is hickelous nydroxide.
Preferably, mixture of the adhesive for polytetrafluoroethylene (PTFE) and butadiene-styrene rubber composition.
Preferably, conductive agent is the cobalt powder that average grain diameter is 0.5~15 μm.
Preferably, the content of cobalt powder is the 6wt% of positive electrode total amount.
Preferably, the content of additive is 1~3wt% of positive electrode total amount.
Preferably, additive is that each component ratio is：Titanium oxide：Calcirm-fluoride：Praseodymium neodymium oxides=20~25:45~60: 15~20.
Example IV：
A kind of positive electrode of Ni-MH battery, including positive electrode, positive electrode includes active material, conductive agent, bonding Agent, additive.
Preferably, active material is hickelous nydroxide.
Preferably, mixture of the adhesive for polytetrafluoroethylene (PTFE) and butadiene-styrene rubber composition.
Preferably, conductive agent is the cobalt powder that average grain diameter is 0.5~15 μm.
Preferably, the content of cobalt powder is the 8wt% of positive electrode total amount.
Preferably, the content of additive is 1~3wt% of positive electrode total amount.
Preferably, additive is that each component ratio is：Titanium oxide：Calcirm-fluoride：Praseodymium neodymium oxides=20~25:45~60: 15~20.
Embodiment five：
A kind of positive electrode of Ni-MH battery, including positive electrode, positive electrode includes active material, conductive agent, bonding Agent, additive.
Preferably, active material is hickelous nydroxide.
Preferably, mixture of the adhesive for polytetrafluoroethylene (PTFE) and butadiene-styrene rubber composition.
Preferably, conductive agent is the cobalt powder that average grain diameter is 0.5~15 μm.
Preferably, the content of cobalt powder is the 10wt% of positive electrode total amount.
Preferably, the content of additive is 1~3wt% of positive electrode total amount.
Preferably, additive is that each component ratio is：Titanium oxide：Calcirm-fluoride：Praseodymium neodymium oxides=20~25:45~60: 15~20.Positive electrode obtained by above-mentioned five embodiments is subjected to capacitance and discharge voltage stability test, is obtained Discharge voltage figure as shown in Figure 1, capacitance parameter as shown in following table one,
The relationship of table one, cobalt powder content and positive electrode capacitance
Cobalt powder content/(wt%) Specific discharge capacity/(mAhg-1)
Embodiment one 2 303
Embodiment two 4 311
Embodiment three 6 315
Example IV 8 322
Embodiment five 10 330
Comparative example one 0 281
Wherein, the conductive agent in comparative example one is acetylene black, other substances and ratio are identical with embodiment one；Comparative example Additive in two is zinc oxide, other substances and ratio are identical with embodiment one.
Table one is observed, the specific discharge capacity relative contrast example one for the positive electrode that five embodiments obtain, which has, significantly to be carried Height, with the raising of cobalt powder content, specific discharge capacity is gradually increased.
Observe Fig. 1, it is found that the discharge voltage relative contrast example two of embodiment is more stablized, and is more than in capacitance When 10%, remain that voltage is more than 1.2V.
Embodiment described above only expresses five kinds of embodiments of the present invention, and description is more specific and detailed, but simultaneously Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (7)

1. a kind of positive electrode of Ni-MH battery, including positive electrode, the positive electrode includes active material, conductive agent, glues Mixture, additive, which is characterized in that the conductive agent is cobalt powder, one kind in cobalt oxide, cobalt protoxide, and the additive is Titanium oxide, calcirm-fluoride, praseodymium neodymium oxides composition.
2. the positive electrode of a kind of Ni-MH battery according to claim 1, which is characterized in that the content of the conductive agent is 2~10wt% of positive electrode total amount.
A kind of 3. positive electrode of Ni-MH battery according to claim 1 or 2, which is characterized in that the conductive agent powder Average grain diameter be 0.5~15 μm.
4. the positive electrode of a kind of Ni-MH battery according to claim 1, which is characterized in that the content of the additive is 1~3wt% of positive electrode total amount.
5. a kind of positive electrode of Ni-MH battery according to claim 1 or 4, which is characterized in that the additive it is each Component ratio is：Titanium oxide：Calcirm-fluoride：Praseodymium neodymium oxides=20~25:45~60:15~20.
6. the positive electrode of a kind of Ni-MH battery according to claim 1, which is characterized in that the active material is hydrogen-oxygen Change sub- nickel.
7. the positive electrode of a kind of Ni-MH battery according to claim 1, which is characterized in that described adhesive is polytetrafluoro The mixture of ethylene and butadiene-styrene rubber composition.
CN201711203064.1A 2017-11-27 2017-11-27 A kind of positive electrode of Ni-MH battery Pending CN108155382A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1216405A (en) * 1998-12-15 1999-05-12 冶金工业部钢铁研究总院 Manufacture of alkaline secondary nickel-hydrogen cell and its positive and negative pole material
CN1702902A (en) * 2005-06-17 2005-11-30 宜兴新兴锆业有限公司 High temperature nickel-hydrogen battery
CN105390755A (en) * 2015-11-05 2016-03-09 衡阳电科电源有限公司 Super-wide-temperature-range nickel-hydrogen battery and manufacturing method therefor
US20170179470A1 (en) * 2015-12-18 2017-06-22 Samsung Electronics Co., Ltd. Composite positive active material, method of preparing the same, positive electrode including the composite positive active material, and lithium battery including the positive electrode

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1216405A (en) * 1998-12-15 1999-05-12 冶金工业部钢铁研究总院 Manufacture of alkaline secondary nickel-hydrogen cell and its positive and negative pole material
CN1702902A (en) * 2005-06-17 2005-11-30 宜兴新兴锆业有限公司 High temperature nickel-hydrogen battery
CN105390755A (en) * 2015-11-05 2016-03-09 衡阳电科电源有限公司 Super-wide-temperature-range nickel-hydrogen battery and manufacturing method therefor
US20170179470A1 (en) * 2015-12-18 2017-06-22 Samsung Electronics Co., Ltd. Composite positive active material, method of preparing the same, positive electrode including the composite positive active material, and lithium battery including the positive electrode

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Application publication date: 20180612