CN101645505A - High-capacity iron electrode material - Google Patents
High-capacity iron electrode material Download PDFInfo
- Publication number
- CN101645505A CN101645505A CN200810046446A CN200810046446A CN101645505A CN 101645505 A CN101645505 A CN 101645505A CN 200810046446 A CN200810046446 A CN 200810046446A CN 200810046446 A CN200810046446 A CN 200810046446A CN 101645505 A CN101645505 A CN 101645505A
- Authority
- CN
- China
- Prior art keywords
- iron
- electrode material
- capacity
- iron electrode
- rare earth
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Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
-
- 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 invention provides a high-capacity iron electrode material, which is characterized by consisting of an active matter and an additive. The active matter is iron or a compound of iron and comprisesone or more of Fe3O4, Fe(OH)2, Fe(OH)3, Fe2O3, reduced iron powder, and carbonyl iron powder; and the additive comprises 1) 1 to 10 percent of rare earth oxides and 2) 1 to 3 percent of nickel hydroxide or saturated nickel sulfate solution, wherein the rare earth oxides comprise one or more of La2O3, CeO2, Nd2O3, Pr2O3, Y2O3, Gd2O3, Sm2O3 and the like. The iron electrode material has the advantages that: 1) poisonous heavy metals (such as Hg, Cd, Pb and the like) are not added, so that the iron electrode material is an environmental protection type electrode material; 2) precious metals (suchas In, Ga and the like) are not added, so the cost of the iron electrode material is extremely low; and 3) the capacity of the active matter of the electrode exceeds 400mAh/g. The material is used formanufacturing high-energy environment-protecting iron-nickel batteries.
Description
Technical field
The present invention relates to a kind of iron electrode material, particularly relate to a kind of high-capacity iron electrode material, this electrode material is used to make high-energy environmental protection Hawkins cell.
Background technology
Hawkins cell is that Edison was invention in 1900.1910 between nineteen sixty, Hawkins cell is widely used in traction locomotive as electrical source of power.But after nineteen sixty, people reduce to some extent to the research of Hawkins cell, and main cause is that ickel-cadmium cell has than iron nickel more performance.Along with the continuous progress of society, people are also more and more higher to requirement on environmental protection, and originally ickel-cadmium cell that heavy metal pollution is arranged of Cai Yonging and lead-acid battery will be replaced by the battery of environment-friendly type, and Hawkins cell has just in time satisfied this requirement.
Hawkins cell belongs to the environmental protection secondary cell, this battery be compound with iron or iron as negative electrode active material, hickelous nydroxide is a positive active material, NaOH (potassium) aqueous solution is electrolyte.According to preparation technology's difference of electrode, Hawkins cell is divided into two types on bag-type battery and board-like battery.The characteristics of bag-type battery are that the life-span is very long, but specific energy is lower, and board-like battery is just in time opposite, and relative pocket type of life-span will hang down, but specific energy is higher.Compare with ickel-cadmium cell with traditional lead-acid battery, Hawkins cell has tangible advantage: does not pollute environment (1).Poisonous heavy metal elements such as the used material of Hawkins cell is all not mercurous, lead and cadmium do not have poisonous gas and water generates yet in the production process.(2) life-span is very long.The life-span of ickel-cadmium cell is greater than 500 times, and the life-span of lead-acid battery is greater than 250 times, and the life-span of board-like Hawkins cell can surpass 900 times, and the life-span of pocket type Hawkins cell can reach 2000-4000 time, and can reach 10-25 service time.(3) theoretical specific energy height.The positive pole of Hawkins cell is anodal identical with ickel-cadmium cell and Ni-H cell, but the theoretical capacity of the ferroelectric utmost point is 2.67 times of cadmium electrode theoretical capacity up to 1280mAh/g, is 3.56 times of metal hydride cell theoretical capacity.(4) moderate cost.In all electrode materials, the price of iron is the most cheap.Compare with lithium ion battery with Ni-H cell, Hawkins cell also has the very low characteristics of price.Compare with lead-acid battery, though the price of Hawkins cell is high slightly, the life-span of its overlength can remedy this part price that exceeds fully.But yet there are some problems in Hawkins cell, comprising: the self discharge of (1) battery is big.(2) heavy-current discharge and low temperature performance are relatively poor.(3) charge efficiency of battery is lower.(4) active material utilization of the ferroelectric utmost point is low.Generally has only 10-20%.This has just greatly limited the raising of Hawkins cell specific energy.These problems all cause owing to the ferroelectric utmost point.Patent CN1532965A has proposed a kind of method that overcomes ferroelectric utmost point shortcoming, is to put into Al-Sn-Ga in ferroelectric adding in extremely.Kind electrode has lower self discharge and higher charge efficiency, but discharge capacity has only 180mAh/g, can not satisfy the needs of high energy battery, and is added with this precious metal element of Ga in the electrode, and the cost of electrode is also higher.
Summary of the invention
The object of the invention is to solve the low problem of ferroelectric utmost point active material utilization, provide a kind of high power capacity iron electrode material, the kind electrode material capacity surpasses 400mAh/g, and need not add noble metal, does not also have the pollution of heavy metal.
High-capacity iron electrode material of the present invention is made up of active material and additive.The composition of active material is the compound of iron or iron, comprises Fe
3O
4, Fe (OH)
2, Fe (OH)
3, Fe
2O
3, reduced iron powder, one or more in the carbonyl iron dust; Additive comprises: 1) content is the rare earth oxide of 1-10%, and rare earth oxide comprises La
2O
3, CeO
2, Nd
2O
3, Pr
2O
3, Y
2O
3, Gd
2O
3, Sm
2O
3Deng in one or more, 2) content is hickelous nydroxide or the saturated nickel sulfate solution of 1-3%.Because directly the iron compound impurity content of buying is higher, active very poor, therefore generally need preparation voluntarily.Illustrate active material Fe
3O
4The preparation method: (1) is with purifying waste water and technical grade ferrous sulfate preparation density is 1.24-1.26g/cm
3Copperas solution.(2) preparing density with purifying waste water with technical grade NaOH is 1.13-1.15g/cm
3Sodium hydroxide solution.(3) copperas solution is heated to 90-98 ℃, the mode of sodium hydroxide solution with spray joined in the copperas solution, in solution, blast air simultaneously.(4) treat that sodium hydroxide solution adds after, add the acetylene black of ferrous sulfate content 1-5%, blast air half an hour again.(5) filter the slurry of gained with canvas of chemical fibre, and with the extremely sulfur-bearing acid group not of washing precipitation of purifying waste water.(6) will precipitate oven dry after, be put under 780-880 ℃ the condition and reduce.(7) material after will reducing was crushed to 20 mesh sieves, obtained needed ferroelectric utmost point active material.
Compare with the common ferroelectric utmost point, the advantage of the ferroelectric utmost point of the present invention is the capacity height, surpasses 400mAh/g.
Description of drawings
Fig. 1: high-capacity iron electrode material and common iron electrode material are at 25 ℃ of following 0.2C (60mA/g) discharge curve.
Embodiment
Embodiment: the chemical composition of high-capacity iron electrode material of the present invention is:
The Fe that makes by above-mentioned side
3O
4Content is 88-92%, and the content of yittrium oxide is 3-5%., and the content of saturated nickel sulfate solution is 1-3%, and the content of graphite powder is 2-5%.
The preparation method of the ferroelectric utmost point is: (1) takes by weighing a certain amount of Fe
3O
4, press Fe
3O
4Amount place the yittrium oxide of 3-5%.(2) in dry powder, add the nickelous sulfate saturated solution of 1-3% and the graphite powder of 2-5%.(3) adding a certain amount of concentration again is the 5-10%PVA binding agent, after stirring, slurry is coated on the negative current collector (collector be in nickel foam, foam iron or the nickel plating Punching steel strip a kind of).(4) with after the electrode oven dry, the pressure with 24MPa on hydraulic press is molded with electrode.
The ferroelectric utmost point discharge and recharge test: with the above-mentioned ferroelectric utmost point that makes as work electrode, sintered type hydroxide nickel electrode is an auxiliary electrode, and the capacity of auxiliary electrode is considerably beyond the capacity of the ferroelectric utmost point, therefore can be with auxiliary electrode as reference electrode, electrolyte is the 6mol/L KOH solution (LiOH.H that wherein contains 15g/L
2O), barrier film is a polypropylene mat.Electrochemical property test equipment is homemade DC-5 type battery performance test instrument.The activation system is to activate 6 times with 0.2C earlier, and ambient temperature is 25 ℃ ± 5 ℃.0.2C during activation, charging current is 100mA/g, charging 6h, and discharging current is 60mA/g, and the discharge stopping potential is 1.0V.The 6th time discharge capacity is the capacity of electrode.
As can be seen from Figure 1, iron electrode material of the present invention surpasses 400mAh/g 25 ℃ of following 0.2C discharge capacities, and common iron electrode material discharge capacity is 187mAh/g.
Claims (3)
1, a kind of high-capacity iron electrode material is characterized in that: this iron electrode material is made up of active material and additive.The composition of active material is the compound of iron or iron.Additive comprises: 1) content is the rare earth oxide of 1-10%, and rare earth oxide comprises La
2O
3, CeO
2, Nd
2O
3, Pr
2O
3, Y
2O
3, Gd
2O
3, Sm
2O
3Deng in one or more; 2) content is hickelous nydroxide or the saturated nickel sulfate solution of 1-3%.
2, high-capacity iron electrode material according to claim 1 is characterized in that: active material can be Fe
3O
4, Fe (OH)
2, Fe (OH)
3, Fe
2O
3, reduced iron powder, one or more in the carbonyl iron dust.
3, high-capacity iron electrode material according to claim 1 is characterized in that: the KOH aqueous solution that its used electrolyte is 6mol/L wherein is added with the LiOH.H of 15g/L
2O.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100464462A CN101645505B (en) | 2008-11-03 | 2008-11-03 | High-capacity iron electrode material |
| PCT/CN2009/074708 WO2010060333A1 (en) | 2008-11-03 | 2009-10-30 | Iron electrode material with high capacity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100464462A CN101645505B (en) | 2008-11-03 | 2008-11-03 | High-capacity iron electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101645505A true CN101645505A (en) | 2010-02-10 |
| CN101645505B CN101645505B (en) | 2011-06-22 |
Family
ID=41657278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100464462A Active CN101645505B (en) | 2008-11-03 | 2008-11-03 | High-capacity iron electrode material |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101645505B (en) |
| WO (1) | WO2010060333A1 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102623757A (en) * | 2012-04-17 | 2012-08-01 | 河南创力新能源科技有限公司 | Iron-nickel storage battery adopting steel-strip iron electrode as cathode and preparation method of iron-nickel storage battery |
| CN102623712A (en) * | 2012-04-17 | 2012-08-01 | 河南创力新能源科技有限公司 | Foamed iron electrode and preparation method thereof |
| CN102623758A (en) * | 2012-04-17 | 2012-08-01 | 河南创力新能源科技有限公司 | Iron-nickel storage battery adopting foamed nickel or iron-type iron electrode as cathode and preparation method of iron-nickel storage battery |
| CN102623710A (en) * | 2012-04-17 | 2012-08-01 | 河南创力新能源科技有限公司 | Foamed iron electrode and preparation method thereof |
| CN102623713A (en) * | 2012-04-17 | 2012-08-01 | 河南创力新能源科技有限公司 | Steel-strip iron electrode and preparation method thereof |
| CN102623759A (en) * | 2012-04-17 | 2012-08-01 | 河南创力新能源科技有限公司 | Iron-nickel storage battery adopting foamed-type iron electrode as cathode and preparation method of iron-nickel storage battery |
| CN102891292A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Method for preparing composite anode material of lithium-sulfur battery |
| CN103219494A (en) * | 2013-03-31 | 2013-07-24 | 马军昌 | Preparation method of graphite-ferroferric oxide composite cathode material |
| CN103579614A (en) * | 2013-11-14 | 2014-02-12 | 哈尔滨工程大学 | Preparation method of lithium ion battery cathode material composited by in-situ synthesis Fe-Fe3O4 |
| CN105684209A (en) * | 2013-09-23 | 2016-06-15 | 南加利福尼亚大学 | A high efficiency nickel-iron battery |
| CN107068991A (en) * | 2017-01-12 | 2017-08-18 | 四川大学 | Iron electrode of the high coulombic efficiency low-temperature rate iron negative material and preparation method thereof with preparation |
| US10393688B2 (en) * | 2011-05-13 | 2019-08-27 | Seiko Epson Corporation | Sensor device |
| CN110931269A (en) * | 2019-12-09 | 2020-03-27 | 河南创力新能源科技股份有限公司 | Capacitive iron-nickel battery iron electrode |
| CN112635715A (en) * | 2020-12-18 | 2021-04-09 | 湖北亿纬动力有限公司 | Lithium ion battery anode slurry, and homogenizing method and application thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2721688B1 (en) | 2011-06-15 | 2018-02-28 | University of Southern California | High efficiency iron electrode and additives for use in rechargeable iron-based batteries |
| US11611115B2 (en) | 2017-12-29 | 2023-03-21 | Form Energy, Inc. | Long life sealed alkaline secondary batteries |
| MX2021000733A (en) | 2018-07-27 | 2021-05-12 | Form Energy Inc | Negative electrodes for electrochemical cells. |
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| US4021911A (en) * | 1976-01-07 | 1977-05-10 | Viktor Evmenievich Kononenko | Method for producing an iron electrode for an alkaline accumulator |
| US4123568A (en) * | 1976-06-01 | 1978-10-31 | Viktor Evmenievich Kononenko | Method of manufacturing an iron electrode for alkaline accumulators |
| DE2837980C2 (en) * | 1978-08-31 | 1983-11-10 | Gerhard Dr. 7301 Deizisau Berger | Activation additive for iron electrodes in alkaline batteries |
| JP2001143745A (en) * | 1999-11-12 | 2001-05-25 | Matsushita Electric Ind Co Ltd | Nickel hydrogen storage battery |
| CN1268779A (en) * | 2000-05-12 | 2000-10-04 | 南开大学 | Positive electrode of accumulator, and its mfg. method and application |
-
2008
- 2008-11-03 CN CN2008100464462A patent/CN101645505B/en active Active
-
2009
- 2009-10-30 WO PCT/CN2009/074708 patent/WO2010060333A1/en active Application Filing
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10393688B2 (en) * | 2011-05-13 | 2019-08-27 | Seiko Epson Corporation | Sensor device |
| CN102623710B (en) * | 2012-04-17 | 2014-07-23 | 河南创力新能源科技有限公司 | Foamed iron electrode and preparation method thereof |
| CN102623713B (en) * | 2012-04-17 | 2015-08-12 | 河南创力新能源科技股份有限公司 | Steel-strip iron electrode and preparation method thereof |
| CN102623757B (en) * | 2012-04-17 | 2014-07-09 | 河南创力新能源科技有限公司 | Iron-nickel storage battery adopting steel-strip iron electrode as cathode and preparation method of iron-nickel storage battery |
| CN102623713A (en) * | 2012-04-17 | 2012-08-01 | 河南创力新能源科技有限公司 | Steel-strip iron electrode and preparation method thereof |
| CN102623759A (en) * | 2012-04-17 | 2012-08-01 | 河南创力新能源科技有限公司 | Iron-nickel storage battery adopting foamed-type iron electrode as cathode and preparation method of iron-nickel storage battery |
| CN102623757A (en) * | 2012-04-17 | 2012-08-01 | 河南创力新能源科技有限公司 | Iron-nickel storage battery adopting steel-strip iron electrode as cathode and preparation method of iron-nickel storage battery |
| CN102623710A (en) * | 2012-04-17 | 2012-08-01 | 河南创力新能源科技有限公司 | Foamed iron electrode and preparation method thereof |
| CN102623712A (en) * | 2012-04-17 | 2012-08-01 | 河南创力新能源科技有限公司 | Foamed iron electrode and preparation method thereof |
| CN102623758A (en) * | 2012-04-17 | 2012-08-01 | 河南创力新能源科技有限公司 | Iron-nickel storage battery adopting foamed nickel or iron-type iron electrode as cathode and preparation method of iron-nickel storage battery |
| CN102623759B (en) * | 2012-04-17 | 2014-11-05 | 河南创力新能源科技有限公司 | Iron-nickel storage battery adopting foamed-type iron electrode as cathode and preparation method of iron-nickel storage battery |
| CN102891292A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Method for preparing composite anode material of lithium-sulfur battery |
| CN103219494A (en) * | 2013-03-31 | 2013-07-24 | 马军昌 | Preparation method of graphite-ferroferric oxide composite cathode material |
| CN105684209A (en) * | 2013-09-23 | 2016-06-15 | 南加利福尼亚大学 | A high efficiency nickel-iron battery |
| CN103579614B (en) * | 2013-11-14 | 2015-06-17 | 哈尔滨工程大学 | Preparation method of lithium ion battery cathode material composited by in-situ synthesis Fe-Fe3O4 |
| CN103579614A (en) * | 2013-11-14 | 2014-02-12 | 哈尔滨工程大学 | Preparation method of lithium ion battery cathode material composited by in-situ synthesis Fe-Fe3O4 |
| CN107068991A (en) * | 2017-01-12 | 2017-08-18 | 四川大学 | Iron electrode of the high coulombic efficiency low-temperature rate iron negative material and preparation method thereof with preparation |
| CN110931269B (en) * | 2019-12-09 | 2021-12-17 | 河南创力新能源科技股份有限公司 | Capacitive iron-nickel battery iron electrode |
| CN110931269A (en) * | 2019-12-09 | 2020-03-27 | 河南创力新能源科技股份有限公司 | Capacitive iron-nickel battery iron electrode |
| CN112635715A (en) * | 2020-12-18 | 2021-04-09 | 湖北亿纬动力有限公司 | Lithium ion battery anode slurry, and homogenizing method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2010060333A1 (en) | 2010-06-03 |
| CN101645505B (en) | 2011-06-22 |
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Assignee: Sichuan constant energy battery Co., Ltd. Assignor: Chengdu Heneng Science and Technology Co., Ltd. Contract record no.: 2011510000317 Denomination of invention: High-capacity iron electrode material Granted publication date: 20110622 License type: Common License Open date: 20100210 Record date: 20111125 Assignee: SICHUAN JIANNENG POWER SUPPLY TECHNOLOGY CO., LTD. Assignor: Chengdu Heneng Science and Technology Co., Ltd. Contract record no.: 2011510000318 Denomination of invention: High-capacity iron electrode material Granted publication date: 20110622 License type: Common License Open date: 20100210 Record date: 20111125 |
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Effective date of registration: 20190904 Address after: 610000 Shenghe Road, Chengdu High-tech Zone, Sichuan Province, No. 88, No. 1, No. 2, Building 20, 2001 Patentee after: Baosheng Group Co. Ltd. Address before: 610000 A310, No. 4 Xixin Avenue, Gaoxin West District, Chengdu City, Sichuan Province Patentee before: Chengdu Heneng Science and Technology Co., Ltd. |