CN100486026C - Alkaline secondary cell using boride as cathode active material - Google Patents
Alkaline secondary cell using boride as cathode active material Download PDFInfo
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- CN100486026C CN100486026C CNB2006101034231A CN200610103423A CN100486026C CN 100486026 C CN100486026 C CN 100486026C CN B2006101034231 A CNB2006101034231 A CN B2006101034231A CN 200610103423 A CN200610103423 A CN 200610103423A CN 100486026 C CN100486026 C CN 100486026C
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- boride
- negative pole
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
This invention provides a high performance alkali secondary battery with boride as the negative material including a negative, a positive, a membrane or polymer electrolyte and alkali electrolyte solution, in which, the boride elements for the negative include M, B, O and H, M is metal selected from Fe, Ti, Cu, Zn, Al, Zr, Nd, Mo, V, Cr, Co, Ni, Ag and Mg, the O and H in the boride are combined with M and B by physical adsorption or chemical bonds, the boride is combined with O or H or both at the same time, the mass sum of M and B is 38.3-99.7% of the total.
Description
Technical field
The invention belongs to secondary battery technology, particularly the technical field of high energy alkaline secondary cell.
Background technology
Though 21 century might progressively be set up the energy resource structure framework based on Hydrogen Energy, but high energy secondary cell technology is also developing rapidly, no matter as " replacement technique " or " transitional technology ", all will in the energy resource structure in future, occupy critical positions and (look into full property work, chemical power source selects opinion, and 2005).Metal hydride/nickel secondary batteries is as the important representative of high energy secondary cell, and the mutual conversion by between chemistry and electrochemical reaction realization Hydrogen Energy and the electric energy combines Hydrogen Energy and high energy secondary cell technology.But the reversible capacity of the AB5 type hydrogen-storage electrode that adopts in metal current hydride/nickel secondary batteries is only for about 280-300mAh/g, and it is very difficult to want continuation its energy density of raising and power density.
Discover that some metal borides have very high hydrogen activity (International Journal of Hydrogen Energy 282003,28:1095; Materials Letters, 2005,59:1748), therefore might be as novel hydrogen storage material.By simple solwution method, can obtain highly active metal boride (CN1616147A).In addition, the structural characterization that boronation cobalt after the treatment of different temperature carries out is found, predecessor by amorphous state in the crystalline state transforming process, experienced the change procedure of (metal boride → metal boride+metal → metal), and closely related (the Materials Letters of this structural change process of the hydrogen activity of material and metal boride, 2005,59:1748).What we were nearest studies show that, is negative pole with the metal boride, and the nickel hydroxide that applies or be compressed on nickel foam or the sintrered nickel is anodal, is assembled into alkaline secondary cell, can obtain high power capacity and excellent cycle performance.
Summary of the invention
The object of the present invention is to provide a kind of is the alkaline secondary cell of negative active core-shell material with the boride, and the negative active core-shell material of this alkaline secondary cell is a boride.Described boride has electro-chemical activity height, various, the preparation technology's characteristic of simple of preparation method.
For achieving the above object, provided by the invention is that the composition of the alkaline secondary cell of negative active core-shell material comprises negative pole, positive pole, barrier film, alkaline aqueous solution or polymer dielectric with the boride; Wherein just very apply or be compressed on the nickel hydroxide on nickel foam or the sintrered nickel; Separate by barrier film or polymer dielectric between positive pole and the negative pole; Anodal being picked out with the battery case two ends of mutually insulated by lead-in wire respectively with negative pole links to each other.
Of the present invention is that the negative pole of the alkaline secondary cell of negative active core-shell material is made up of boride, binding agent and conductive agent with the boride, and negative active core-shell material is a boride, and negative pole applies or is compressed on afflux and extremely goes up, and is soaked in the alkaline aqueous solution.
The feature of described boride comprises:
(1) element of boride is formed and is comprised M, B, O and H, and wherein M is a metallic element, and M is selected among Fe, Ti, Cu, Zn, Al, Zr, Nd, Mo, V, Cr, Co, Ni, Ag, the Mg one or more;
(2) O in the boride and H combine with M and B by physical absorption or chemical bond.Boride or be combined with O, or be combined with O and H simultaneously;
(3) the quality sum of M and B accounts for the 38.3-99.7% of boride gross mass in the boride.
Described boride can synthesize by several different methods, and these methods comprise reducing process, ball-milling method, roasting method, the precipitation method, arc process.
Of the present invention is that binding agent in the alkaline secondary cell of negative active core-shell material is selected from one or more in Kynoar, polytetrafluoroethylene, polyacrylate, methylcellulose, polymethacrylates, the polyvinyl alcohol with the boride;
Conductive agent is selected from one or more in metal oxide, carbonaceous mesophase spherules, metal powder, acetylene black, graphite, the alloyed powder;
When the conductivity of the boride for preparing is good, also can not use conductive agent in the negative pole;
The negative pole currect collecting utmost point is selected from a kind of in wire netting, metal forming, carbon cloth, carbon paper, the nickel foam;
The concentration of alkaline aqueous solution is 2-8mol/l, and electrolytic salt wherein is selected from one or more among KOH, NaOH, the LiOH.
Description of drawings
Accompanying drawing one is the discharge capacity figure that presses embodiment 2 described alkaline secondary cells,
Wherein transverse axis is represented cycle-index; The longitudinal axis is represented discharge capacity, and unit is mAh/g.
Embodiment
Describe the present invention in detail below by specific embodiment:
Embodiment 1
Get 2.45 gram metal Ni, 1.26 gram metal Fe, 0.23 gram B places ball grinder under nitrogen atmosphere, and ball milling after 40 hours takes out product.Through inducing the coupling plasma spectroscopy, the quality sum of Ni, Fe and B accounts for 99.7% of boride gross mass in the gained boride, and the quality of O accounts for 0.3%.
With the boride of gained, as the polytetrafluoroethylene of binding agent, mix as the Ni powder of conductive agent mass ratio by 80:5:15, roll film forming, make sheet with the afflux extreme pressure then and make negative pole.
Prepared negative pole and the nickel hydroxide positive plate that is compressed on the nickel foam are assembled into alkaline secondary cell, and electrolyte adopts the alkaline aqueous solution of 8mol/l, and wherein KOH concentration is 7.9mol/l, and LiOH concentration is 0.1mol/l.The negative pole of alkaline secondary cell and anodal the immersion in electrolyte after 24 hours charge and discharge carrying out constant current with the current density of 10mA/g by discharging and recharging of computer control on the instrument, and the discharge capacity that records reaches 306mAh/g, and has excellent cycle performance.
Get concentration and be 10% CoCl
2Solution 40ml places flask, is 5% NaBH then with 100ml concentration
4Solution joins in the flask; In this process, the solution in the flask is carried out sonic oscillation.Reaction stops sonic oscillation after finishing, and makes the suspension-turbid liquid layering.Supernatant liquor is removed; The lower sediment thing is taken out, with deionized water wash, suction filtration.The sediment that above-mentioned suction filtration is crossed obtains unbodied boride after 40 ℃ of following vacuumize.The quality sum of Co and B accounts for 38.3% of boride gross mass in the gained boride, and O and H account for 61.7%.
With the boride of gained, as the Kynoar of binding agent, mix by the mass ratio of 85:5:10 as the CoO of conductive agent, roll film forming, make sheet with the afflux extreme pressure then and make negative pole.
Prepared negative pole and the nickel hydroxide positive plate that is compressed on the nickel foam are assembled into alkaline secondary cell, and electrolyte adopts the KOH aqueous solution of 6mol/l.The negative pole of alkaline secondary cell and positive pole soak after 48 hours in electrolyte, charge and discharge carrying out constant current with the current density of 30mA/g on the instrument by discharging and recharging of computer control, the discharge capacity that records reaches 342mAh/g, and have excellent cycle performance, its discharge capacity with the change curve of cycle-index as shown in drawings.
Embodiment 3
Getting concentration is 10%NiCl
2Solution 50ml places flask, is 5% NaBH then with 160ml concentration
4Solution joins in the flask; In this process, the solution in the flask is carried out magnetic agitation.After reaction finishes, stop stirring and make the suspension-turbid liquid layering.Supernatant liquor is removed; The lower sediment thing is taken out, with deionized water wash, suction filtration.The sediment that above-mentioned suction filtration is crossed continues 650 ℃ of heating 2 hours down after 100 ℃ of following vacuumize, after the cooling boride.The quality sum of Ni and B accounts for 91.2% of boride gross mass in the above-mentioned boride, and O and H account for 8.8%.
With the boride of gained, as the Kynoar of binding agent, mix as the Ni powder of conductive agent mass ratio by 80:5:10, roll film forming, make sheet with the afflux extreme pressure then and make negative pole.
Prepared negative pole and the nickel hydroxide positive plate that is compressed on the nickel foam are assembled into alkaline secondary cell, and electrolyte adopts the KOH aqueous solution of 2mol/l.The negative pole of alkaline secondary cell and anodal the immersion in electrolyte after 48 hours charge and discharge carrying out constant current with the current density of 20mA/g by discharging and recharging of computer control on the instrument, and the discharge capacity that records reaches 225mAh/g, and has excellent cycle performance.
Embodiment 4
Get the CoCl of 0.5mol/l
2The MgCl of solution 100ml and 0.5mol/l
2Solution 50ml places flask, is the NaBH of 1mol/l then with 270ml concentration
4Solution joins in the flask; In this process, the solution in the flask is carried out magnetic agitation.After reaction finishes, stop stirring and make the suspension-turbid liquid layering.Supernatant liquor is removed; The lower sediment thing is taken out, with deionized water wash, suction filtration.The sediment that above-mentioned suction filtration is crossed continues 480 ℃ of heating 8 hours down after 70 ℃ of following vacuumize, after the cooling boride.The quality sum of Co, Mg and B accounts for 85.7% of boride gross mass in the above-mentioned boride, and O and H account for 14.3%.
With the boride of gained, mix as the mass ratio of the Kynoar 90:10 of binding agent, do not add conductive agent, roll film forming, make sheet with the afflux extreme pressure then and make negative pole.
Prepared negative pole and the nickel hydroxide positive plate that is compressed on the nickel foam are assembled into alkaline secondary cell, and electrolyte adopts the KOH aqueous solution of 6mol/l.The negative pole of alkaline secondary cell and anodal the immersion in electrolyte after 48 hours charge and discharge carrying out constant current with the current density of 20mA/g by discharging and recharging of computer control on the instrument, and the discharge capacity that records reaches 317mAh/g, and has excellent cycle performance.
Claims (3)
1. one kind is the alkaline secondary cell of negative active core-shell material with the boride, forms to comprise negative pole, positive pole, barrier film, alkaline aqueous solution or polymer dielectric; Wherein just very apply or be compressed on the nickel hydroxide on nickel foam or the sintrered nickel; Separate by barrier film or polymer dielectric between positive pole and the negative pole; Anodal being picked out with the battery case two ends of mutually insulated by lead-in wire respectively with negative pole links to each other; It is characterized in that: used negative active core-shell material is a boride, and negative pole is made up of boride, binding agent and conductive agent, and negative pole applies or is compressed on afflux and extremely goes up, and is soaked in the alkaline aqueous solution;
The feature of described boride comprises:
(1) element of boride is formed and is comprised M, B, O and H, and wherein M is a metallic element, and M is selected among Fe, Ti, Cu, Zn, Al, Zr, Nd, Mo, V, Cr, Co, Ni, Ag, the Mg one or more;
(2) O in the boride and H combine with M and B by physical absorption or chemical bond; Boride or be combined with O, or be combined with O and H simultaneously;
(3) the quality sum of M and B accounts for the 38.3-99.7% of boride gross mass in the boride.
By claim 1 described a kind of be the alkaline secondary cell of negative active core-shell material with the boride, it is characterized in that: the synthetic method of described boride is a kind of in reducing process, ball-milling method, roasting method, the precipitation method, the arc process; Described binding agent is selected from one or more in Kynoar, polytetrafluoroethylene, polyacrylate, methylcellulose, polymethacrylates, the polyvinyl alcohol; Described conductive agent is selected from one or more in metal oxide, carbonaceous mesophase spherules, metal powder, acetylene black, graphite, the alloyed powder; The described negative pole currect collecting utmost point is selected from a kind of in wire netting, metal forming, carbon cloth, carbon paper, the nickel foam; The concentration of described alkaline aqueous solution is 2-8mol/l, and electrolytic salt wherein is selected from one or more among KOH, NaOH, the LiOH.
By claim 1 described a kind of be the alkaline secondary cell of negative active core-shell material with the boride, it is characterized in that: do not use conductive agent in the negative pole.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006101034231A CN100486026C (en) | 2006-07-20 | 2006-07-20 | Alkaline secondary cell using boride as cathode active material |
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| CNB2006101034231A CN100486026C (en) | 2006-07-20 | 2006-07-20 | Alkaline secondary cell using boride as cathode active material |
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| CN1901265A CN1901265A (en) | 2007-01-24 |
| CN100486026C true CN100486026C (en) | 2009-05-06 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102024981A (en) * | 2010-11-16 | 2011-04-20 | 成都振中电气有限公司 | High-energy secondary battery |
| CN109850912B (en) * | 2019-02-12 | 2022-07-22 | 武汉理工大学 | Alkaline aqueous solution electrolyte system battery positive electrode material of composite bimetal boride 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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Non-Patent Citations (2)
| Title |
|---|
| Nanoparticles produced by borohydride as precursors formetal hydride electrodes. M.Mitov,A.Popov,I.Dragieva.J.Appl.Electrochem.,Vol.29（1） . 1999 |
| Nanoparticles produced by borohydride as precursors formetal hydride electrodes. M.Mitov,A.Popov,I.Dragieva.J.Appl.Electrochem.,Vol.29（1） . 1999 * |
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