CN1492526A - Use of boron-containing transition metal compound as cell negative pole material - Google Patents

Use of boron-containing transition metal compound as cell negative pole material Download PDF

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Publication number
CN1492526A
CN1492526A CNA031254004A CN03125400A CN1492526A CN 1492526 A CN1492526 A CN 1492526A CN A031254004 A CNA031254004 A CN A031254004A CN 03125400 A CN03125400 A CN 03125400A CN 1492526 A CN1492526 A CN 1492526A
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Prior art keywords
metal compound
boracic
capacity
negative
transition metal
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CNA031254004A
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CN1228870C (en
Inventor
杨汉西
王雅东
艾新平
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Wuhan University WHU
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Wuhan University WHU
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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

This invention relates to a new usage for a transient metal compound containing B, concretely, to the usage of the compound containing B as the battery negative material. The discharge capacity is far more higher than that of Zn battery at the present market, its specific capacity reaches to 400mAH/g-1300AH/g in terms of negative material active capacity to realize miniaturization and high capacity.

Description

The boracic transistion metal compound is as the application of cell negative electrode material
Technical field
The present invention relates to a kind of new purposes of boracic transistion metal compound, relate in particular to of the application of boracic transistion metal compound as cell negative electrode material.
Background technology
Aqueous solution battery system is widely used with performance, fail safe and the cheap price of its good discharge, and that occupy main share at present on market is Zn-MnO 2Primary cell.Yet along with development of modern science and technology, various portable electric appts strengthen day by day for the requirement of the specific energy of chemical power source, Zn-MnO 2Though system has obtained breakthrough progress in recent years on performance,, fundamentally limited the further raising of its specific energy because its theoretical capacity is lower.U.S. Steven in 2002 and Amendola have proposed with high-specific energy battery system (the USPat NO.5 of binary boride as negative pole, 948,558), yet by research for polynary boracic metallic compound, we think can also be applied to the negative active core-shell material of electrochemical field as the height ratio capacity battery except can be used as by bibliographical information by polynary boracic metallic compound the catalyst.
Summary of the invention
The object of the present invention is to provide a kind of new purposes of boracic transistion metal compound, this boracic transistion metal compound can discharge the height ratio capacity electric energy as cell negative electrode material.
Technical scheme provided by the invention is the application of boracic transistion metal compound as cell negative electrode material.
The general formula of above-mentioned boracic transistion metal compound: M xB yO z, wherein M represents one or more transition metal, x: y: z=(0.2-5): (0.1-20): (0.05-5).
Above-mentioned boracic transistion metal compound can be made by laxative remedy: the alkali metal borohydride of 0.1-5M, progressively be added dropwise in the aqueous solution of the transition metal saline solution of 0.1-5M or transition metal salt mixture, after the black precipitate process filtering and washing that is generated, the passivation, after 50-120 ℃ of vacuumize, promptly obtain the boracic transistion metal compound.
The present invention adopts the boracic transistion metal compound as cell negative electrode material, and the discharge capacity of the cell that obtains is far above the Zn battery at present leading market, and with the active calculation of capacity of negative material, specific capacity can reach 400mAH/g-1300mAH/g; Therefore can realize miniaturization and high power capacity, satisfy the demand of modern electronic equipment better.
Description of drawings
Fig. 1 is the discharge curve that the present invention obtains by embodiment 1, and air electrode is as the negative pole of battery;
Fig. 2 is the discharge curve that obtains by embodiment 2, and air electrode is as the negative pole of battery;
Fig. 3 is the discharge curve that obtains by embodiment 3, and air electrode is as the negative pole of battery;
Fig. 4 is the discharge curve that obtains by embodiment 4, and air electrode is as the negative pole of battery;
Fig. 5 is the discharge curve that obtains by embodiment 5, and air electrode is as the negative pole of battery;
Fig. 6 is the discharge curve that obtains by embodiment 6, and air electrode is as the negative pole of battery.
Embodiment
The present invention adopts the boracic transistion metal compound as cell negative electrode material, and the aqueous solution battery system that obtains comprises:
1. negative pole: its composition comprises: M xB yO z, wherein M represents transition metal, can be more than one transition metals; X: y: z=(0.2-5): (0.1-20): (0.05-5).
Wherein the boracic transistion metal compound is the compound of transition metal salt through boracic, transition metal and the oxygen of boron hydrogen root reduction back generation, can be expressed as:
Electric conducting material is graphite, acetylene black etc.
Binding agent is a polytetrafluoroethylene etc.
The boracic transistion metal compound is the product that known technology obtains, its concrete preparation method is as follows: the alkali metal borohydride of 0.1-5M, progressively be added dropwise in transition metal salt (for a certain proportion of mixture that is prepared as transition metal salt of the polynary transition metal boron-containing compound) aqueous solution of 0.1-5M, the black precipitate that is generated promptly obtains the boracic transistion metal compound after washing suction filtration, passivation through distilled water after 50-120 ℃ of vacuumize.
2. anodal: air electrode or oxide electrode, its composition comprises: metal oxide, Catalytic Layer, waterproof ventilative layer and currect collecting net, wherein metal oxide is cobalt oxide, manganese oxide etc. or its mixture.
3. electrolyte: be the aqueous solution of 10-40wt% alkali.
The invention will be further described below in conjunction with specific embodiment:
Embodiment 1
NaBH with 0.25M 4Solution 700mL is added dropwise to 500mL 0.2M and is in FeSO in the frozen water territory 4In the solution, after finishing, reaction leaves standstill, suction filtration, and with distilled water washing back acetone passivation, last vacuumize slowly cooled to room temperature in 10 hours and obtains negative active core-shell material (Fe earlier 1.75B 1O 1).
Get the negative material 85% for preparing, acetylene black 8%, polytetrafluoroethylene 7% mixed rolling film forming is then with the compound negative plate that obtains of metal collector.The anodal air electrode of using, electrolyte is 30% the KOH aqueous solution, form simulated battery, the discharge curve of gained battery is seen Fig. 1, capacity among the figure calculates with negative active core-shell material, therefrom the specific capacity of synthetic material is 1.5 times of Zn electrode theoretical capacity, far above the actual discharge capacity of Zn up to 1300mAH/g as can be seen.
Embodiment 2
NaBH with 0.25M 4Solution 700mL is added dropwise to 500mL 0.2M and is in CoSO in the frozen water territory 4In the solution, after finishing, reaction leaves standstill, suction filtration, and with distilled water washing back acetone passivation, last vacuumize slowly cooled to room temperature in 10 hours and obtains negative material (Co earlier 1.19B 1O 0.76).
Get the negative material 85% for preparing, acetylene black 8%, polytetrafluoroethylene 7% mixed rolling film forming is then with the compound negative plate that obtains of metal collector.The anodal air electrode, electrolyte use is 30% the KOH aqueous solution, the composition simulated battery, and the discharge curve of gained battery is seen Fig. 2.As can be seen from the figure with the negative active core-shell material calculation of capacity, the specific capacity of institute's synthetic material can reach and be higher than 900mAH/g, is higher than the theoretical specific capacity that the Zn electrode can't be broken through.
Embodiment 3
NaBH with 0.25M 4Solution 700mL is added dropwise to 500mL 0.2M and is in NiSO in the frozen water territory 4In the solution, after finishing, reaction leaves standstill, suction filtration, and with distilled water washing back acetone passivation, last vacuumize slowly cooled to room temperature in 10 hours and obtains negative material (Ni earlier 1.81B 1O 2.1).
Get the negative material 85% for preparing, acetylene black 8%, polytetrafluoroethylene 7% mixed rolling film forming is then with the compound negative plate that obtains of metal collector.The anodal air electrode, electrolyte use is 30% the KOH aqueous solution, the composition simulated battery, and the discharge curve of gained battery is seen Fig. 3.As can be seen from the figure with the negative active core-shell material calculation of capacity, the specific capacity of institute's synthetic material can reach 400mAH/g, is higher than the actual discharge capacity of Zn electrode under the same terms.
Embodiment 4
NaBH with 0.25M 4Solution 1000 adds the 500mL 0.5M FeSO that is in the frozen water territory 4With 5ml 1mol/LCrCl 3Mixed solution, reaction is left standstill after finishing, suction filtration, with distilled water washing back acetone passivation, vacuumize at last slowly cooled to room temperature in 10 hours and obtains negative material (Fe earlier 1.52Cr 0.3B 1O 1.7).
Get the negative material 85% for preparing, acetylene black 8%, polytetrafluoroethylene 7% mixed rolling film forming is then with the compound negative plate that obtains of metal collector.The anodal air electrode, electrolyte use is 30% the KOH aqueous solution, the composition simulated battery, and the discharge curve of gained battery is seen Fig. 4.As can be seen from the figure with the negative active core-shell material calculation of capacity, the specific capacity of institute's synthetic material can reach more than the 400mAH/g, is higher than the actual discharge capacity of Zn electrode under the same terms.
Embodiment 5
NaBH with 0.25M 4Solution 1000 adds the 400mL 0.5M FeSO that is in the frozen water territory 4With 200ml 0.5mol/LMnSO 4Mixed solution, reaction is left standstill after finishing, suction filtration, with distilled water washing back acetone passivation, vacuumize at last slowly cooled to room temperature in 10 hours and obtains negative material (Fe earlier 1.1Mn 0.2B 3.4O 1).
Get the negative material 85% for preparing, acetylene black 8%, polytetrafluoroethylene 7% mixed rolling film forming is then with the compound negative plate that obtains of metal collector.The anodal air electrode, electrolyte use is 30% the KOH aqueous solution, the composition simulated battery, and the discharge curve of gained battery is seen Fig. 5.As can be seen from the figure with the negative active core-shell material calculation of capacity, the specific capacity of institute's synthetic material can reach more than the 1100mAH/g, is higher than the theoretical discharge capacity of Zn electrode.
Embodiment 6
NaBH with 0.25M 4Solution 1000 adds the 400mL 0.5M FeSO that is in the frozen water territory 4With 200ml 0.5mol/LZrSO 4Mixed solution, reaction is left standstill after finishing, suction filtration, with distilled water washing back acetone passivation, vacuumize at last slowly cooled to room temperature in 10 hours and obtains negative material (Fe earlier 1.3Zr 0.15B 3.45O 1).
Get the negative material 85% for preparing, acetylene black 8%, polytetrafluoroethylene 7% mixed rolling film forming is then with the compound negative plate that obtains of metal collector.The anodal air electrode, electrolyte use is 30% the KOH aqueous solution, the composition simulated battery, and the discharge curve of gained battery is seen Fig. 6.As can be seen from the figure with the negative active core-shell material calculation of capacity, the specific capacity of institute's synthetic material can reach about 1200mAH/g, is higher than the theoretical discharge capacity of Zn electrode.
Embodiment 7
NaBH with 0.25M 4Solution 1000 adds the 400mL 0.5M FeSO that is in the frozen water territory 4, 100ml 0.5mol/LZrSO 4With 100ml 0.5mol/L MnSO 4Mixed solution, reaction is left standstill after finishing, suction filtration, with distilled water washing back acetone passivation, vacuumize at last slowly cooled to room temperature in 10 hours and obtains negative material (Fe earlier 1Zr 0.05Mn 0.04B 16.2O 4.8).
Get the negative material 85% for preparing, acetylene black 8%, polytetrafluoroethylene 7% mixed rolling film forming is then with the compound negative plate that obtains of metal collector.The anodal air electrode, electrolyte use is 30% the KOH aqueous solution, the composition simulated battery, and with the negative active core-shell material calculation of capacity, the specific capacity of institute's synthetic material can reach about 850mAH/g, is higher than the theoretical discharge capacity of Zn electrode.
Embodiment 8
NaBH with 0.25M 4Solution 1000 adds the 400mL 0.5M FeSO that is in the frozen water territory 4, 100ml 0.5mol/LZrSO 4With 100ml 0.5mol/L NiSO 4Mixed solution, reaction is left standstill after finishing, suction filtration, with distilled water washing back acetone passivation, vacuumize at last slowly cooled to room temperature in 10 hours and obtains negative material (Fe earlier 1.2Ni 1.1Zr 0.06B 1O 3.2).
Get the negative material 85% for preparing, acetylene black 8%, polytetrafluoroethylene 7% mixed rolling film forming is then with the compound negative plate that obtains of metal collector.The anodal air electrode, electrolyte use is 30% the KOH aqueous solution, the composition simulated battery, and with the negative active core-shell material calculation of capacity, the specific capacity of institute's synthetic material can reach about 800mAH/g, near the theoretical discharge capacity of Zn electrode.

Claims (3)

1. the boracic transistion metal compound is as the application of cell negative electrode material.
2. purposes according to claim 1 is characterized in that: the general formula of described boracic transistion metal compound: M xB yO z, wherein M represents transition metal, x: y: z=(0.2-5): (0.1-20): (0.05-5).
3. purposes according to claim 2, it is characterized in that: the boracic transistion metal compound is made by laxative remedy: the alkali metal borohydride of 0.1-5M, progressively be added dropwise in the aqueous solution of the transition metal saline solution of 0.1-5M or transition metal salt mixture, the black precipitate that is generated promptly obtains the boracic transistion metal compound after washing suction filtration, passivation through distilled water after 50-120 ℃ of vacuumize.
CNB031254004A 2003-09-10 2003-09-10 Use of boron-containing transition metal compound as cell negative pole material Expired - Fee Related CN1228870C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104638249A (en) * 2015-02-05 2015-05-20 新材料与产业技术北京研究院 Method for preparing anode material electrode plate for high-capacity air battery
CN113314770A (en) * 2021-04-30 2021-08-27 武汉理工大学 Alkaline secondary battery and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104638249A (en) * 2015-02-05 2015-05-20 新材料与产业技术北京研究院 Method for preparing anode material electrode plate for high-capacity air battery
CN104638249B (en) * 2015-02-05 2017-05-10 新材料与产业技术北京研究院 Method for preparing anode material electrode plate for high-capacity air battery
CN113314770A (en) * 2021-04-30 2021-08-27 武汉理工大学 Alkaline secondary battery and preparation method thereof
CN113314770B (en) * 2021-04-30 2023-04-07 武汉理工大学 Alkaline secondary battery and preparation method thereof

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