CN102299323A - Alkaline cell - Google Patents
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- CN102299323A CN102299323A CN201110213204XA CN201110213204A CN102299323A CN 102299323 A CN102299323 A CN 102299323A CN 201110213204X A CN201110213204X A CN 201110213204XA CN 201110213204 A CN201110213204 A CN 201110213204A CN 102299323 A CN102299323 A CN 102299323A
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- 238000000034 method Methods 0.000 claims abstract description 24
- 238000009489 vacuum treatment Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000013049 sediment Substances 0.000 claims description 65
- 239000002245 particle Substances 0.000 claims description 64
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 27
- 239000006258 conductive agent Substances 0.000 claims description 25
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 230000008014 freezing Effects 0.000 claims description 19
- 238000007710 freezing Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
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- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
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- 239000000463 material Substances 0.000 claims description 8
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 235000003642 hunger Nutrition 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052742 iron Inorganic materials 0.000 claims description 4
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- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- -1 wire netting Substances 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 17
- 230000002776 aggregation Effects 0.000 abstract description 4
- 239000007773 negative electrode material Substances 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
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- 239000002243 precursor Substances 0.000 abstract 1
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- 238000007599 discharging Methods 0.000 description 9
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- 238000004080 punching Methods 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 230000005518 electrochemistry Effects 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 206010065042 Immune reconstitution inflammatory syndrome Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101001031591 Mus musculus Heart- and neural crest derivatives-expressed protein 2 Proteins 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000012670 alkaline solution Substances 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
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- 239000002585 base Substances 0.000 description 1
- 239000001996 bearing alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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Images
Classifications
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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
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an alkaline cell, belonging to the field of alkaline cells. Evenly dispersed borides are selected as negative electrode materials of the alkaline cell; and the borides are obtained by thermally treating precursors obtained through solution chemical reaction and cooling-vacuum treatment at low temperature. The alkaline cell with the negative electrode materials has the advantages of high discharge capacity and good cycle performance. In the method for preparing the borides in the negative electrode materials of the alkaline cell, a reactor is placed in an environment with the temperature being minus 20 DEG C to 4 DEG C, thus the temperature of a reaction system can be reduced, and the reaction can be carried out the mildly. The cooling-vacuum treatment at the low temperature is used to restrain the generation of grain agglomeration effectively, thus the borides with high specific area and even grain size distribution are obtained.
Description
Technical field
The present invention relates to a kind of alkaline battery, belong to the alkaline battery field.
Background technology
Along with the continuous lifting of power consumption equipment to the energy and the power requirement of power supply, existing alkaline secondary cell faces great challenge.Wherein the research for Ni/MH cell negative electrode material hydrogen bearing alloy mainly concentrates on AB
5Type rare earth alloy, AB
2Type Laves phase alloy, A
2Type B magnesium base alloy, AB type metallic compound and have on the vanadium radical sosoloid alloy of body-centered cubic structure (Tang Yougen, Ni-MH battery, Chemical Industry Press, 2007).The electrochemistry capacitance of these alloys is on the low side, and has problems such as cost height, difficulty activate, environmental pollution is serious.In view of resource distribution and technology grasp situation, China and Japan factory adopt AB more
5The type rare earth alloy, its electrochemistry capacitance still remains on about 300mAh/g, does not significantly improve, and has limited the Ni/MH battery and has used widely.Therefore, seek the focus that the novel more high performance alkaline battery of electrode material development becomes present research.
Many in recent years research workers find that the transition metal of height inertia in nonacid water solution system is (as V, Ti, Mn etc.) and equally in the boride alloy that the boron of inertia forms, highly electronegative boron element electrochemical stability reduces, help electrochemical oxidation, electrode potential is clamped down on than negative region, caused some transition metal to be in activated state.When above-mentioned boride alloy the polyelectron reaction can take place during as chemistry of aqueous solution power supply (alkalescence or neutral) negative pole, produce extraordinary electrochemistry capacitance (Wu Feng, Chinese material progress, 2009 (28): 41-66).
Boride has high discharge capacity and excellent electrochemical reversibility and receives much concern in alkaline solution.The method of the synthetic boride of having reported has chemical reduction method, ball-milling method, arc melting method, high temperature solid-state method, microemulsion method etc.At present, the researcher generally adopts chemical reduction method to synthesize boride material (M.Mitov, A.Popov, I.Dragieva:Journal of Applied Electrochemistry 1999 (29): 59-63; Wang Y.D., Ai X.P., Cao Y.L.:Electrochemistry Communications, 2004 (6): 780-784), but adopted contain BH
4 -Solution have very strong reproducibility, can heat release during hydrolysis and metal salt solution can the moment reaction, synthetic product exists that particle size is big, particle size distribution is wide, the particle agglomeration phenomenon is serious and shortcoming such as specific area is generally lower.Therefore need provide a kind of negative material uniform particle diameter, specific area is big, discharge capacity is high, the alkaline battery of good cycle.
Summary of the invention
At prior art neutral and alkali battery because the negative material boride exists that particle size is big, particle size distribution is wide, particle agglomeration phenomenon and specific area are generally lower, cause reacting the problem that discharge capacity is lower, cycle performance is relatively poor, the object of the present invention is to provide a kind of alkaline battery.Described alkaline battery has the advantage of discharge capacity height, good cycle.Boride in the described alkaline battery cathode material has that granularity is little, particle size distribution homogeneous, good dispersion, specific area height, activity is high, cheap, raw material obtain easily characteristics.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of alkaline battery, composition comprises: positive plate, negative plate, barrier film and alkaline electrolyte; Or positive plate, negative plate, barrier film and polymer dielectric; Wherein, positive plate is for applying or be suppressed with the collector of hickelous nydroxide; By barrier film or polymer dielectric positive/negative plate is separated; Positive plate and negative plate are picked out by lug respectively; Described negative plate is the collector that is coated with negative material, and negative plate is immersed in the alkaline electrolyte; Described negative material is boride and the mixed uniformly powder of conductive agent;
Wherein, the preparation method of described boride is as follows:
Step 1, the solution that will contain soluble metallic salt add in the reactor, add that excessive to regulate the pH value with alkali or cushioning liquid be 7～14 the BH that contains again
4 -Solution, hybrid reaction obtains sediment 1;
Step 2, with behind sediment 1 usefulness detergent washing 〉=2 time, Separation of Solid and Liquid obtains sediment 2; Then sediment 2 is cooled to below-10 ℃, under vacuum degree≤10.0Pa, carries out vacuum treatment then, obtain predecessor;
Step 3, predecessor is heat-treated under the starvation condition, obtain boride of the present invention;
Wherein, the metallic element in the soluble metallic salt described in the step 1 is one or more among Fe, Ti, Cu, Zn, Al, Zr, Nd, Mo, V, Cr, Co, Ni, Ag or the Mg; Contain BH
4 -Solution in solute be one or more mixture in potassium borohydride, sodium borohydride or the aluminium borohydride; Alkali is one or more the mixture in NaOH, NaOH, lithium hydroxide, ammoniacal liquor, sodium carbonate, sodium acid carbonate, potash, saleratus, calcium hydroxide, barium hydroxide, potassium dihydrogen phosphate or the sodium hydrogen phosphate; Cushioning liquid is a kind of in ammoniacal liquor-chloride buffer solution, borax-calcium chloride cushioning liquid or the borax-sodium carbonate cushioning liquid;
Washing agent in the step 2 is distilled water, deionized water, absolute ethyl alcohol, ethylene glycol, isopropyl alcohol, acetone or methylethylketone; Can wash respectively with identical or different washing agent during washing; Vacuum processing time is 1h～48h;
Heat treatment temperature is 50 ℃～850 ℃ in the step 3, and heat treatment time is 1～48h;
The chemical formula of the boride for preparing with said method is MxB, wherein M is one or more metallic elements among Fe, Ti, Cu, Zn, Al, Zr, Nd, Mo, V, Cr, Co, Ni, Ag or the Mg, 1≤x≤4, and x can be non-integer, described boride is for all disperseing boride.
Wherein, add in the preferred steps one that to regulate the pH value with alkali or cushioning liquid be 7～14 the BH that contains
4 -Solution, be to drip with the speed of 1mL/min～20mL/min; Drip and finish back continuation mixing 0.5h～1h; Mixing condition is that supersonic oscillations, glass bar stir, a kind of in electronic stirring or the magnetic agitation.
Wherein, in the preferred steps one reactor is placed-20 ℃～4 ℃ environment.
Wherein, the process of in the preferred steps two sediment 2 being reduced to below-10 ℃ is: sediment 2 is put into cold-trap, be cooled to-10 ℃～-200 ℃ with cold-trap, rate of temperature fall is 5～90 ℃/min; Cooling time is 1h～12h.
Wherein, the process of in the preferred steps two sediment 2 being reduced to below-10 ℃ is: condenser temperature is reduced to-10 ℃～-200 ℃, sediment 2 placed 〉=1 hour in the liquid nitrogen of 0 ℃～-20 ℃ refrigerator or-196 ℃～-209 ℃ after, put into the freezing 1h～12h of cold-trap after the cooling.
Wherein, in the preferred steps three the starvation condition for charging into inert gas or vacuum degree≤10.0Pa; Inert gas is Ar gas or N
2Gas.
Wherein, the structural form of described boride is crystalline state or amorphous state.
Wherein, the particle diameter of described boride is 2nm～50 μ m; The specific area of described boride is 5m
2/ g～200m
2/ g.
Wherein, described lug is preferably a kind of in nickel strap, aluminium strip or the nickel aluminium strip; Described conductive agent is the general conductive agent in alkaline battery field, is preferably: one or more mixture in nickel powder, cobalt oxide powder, acetylene black, carbon black, graphite powder, carbon nano-tube or the Graphene; Described collector is the general collector in alkaline battery field, is preferably: a kind of in nickel foam, nickel screen, nickel foil, carbon cloth or the carbon paper; The solvent of described alkaline electrolyte is a water, and solute is one or more the mixture among KOH, NaOH or the LiOH, and concentration is 2-8mol/L.
Beneficial effect
1. a kind of alkaline battery of the present invention, the discharge capacity height, cycle performance is good; In the described alkaline battery cathode material preparation method of boride have the early stage be swift in response, subsequent processes is simple and convenient, workable advantage;
2. preparation method of the present invention contains BH by dropping in the step 1
4 -Solution and drip to finish the back and continue to stir, reaction is carried out fully;
3. preparation method of the present invention, hybrid reaction obtains sediment 1 and is exothermic reaction in the step 1, reactor is placed-20 ℃～4 ℃ environment, can reduce the temperature of reaction system, make reaction temperature and carry out, prevent that the particle of sediment 1 from reuniting the growth change greatly because of heat;
4. preparation method of the present invention, make sediment 2 at first be in frozen state by refrigerating process in the step 2, pass through vacuum treatment then, make that liquid is removed by sublimation process in the sediment 2, avoided the hole collapse phenomenon that caused because of the capillary effect of solid liquid interface, the institutional framework and the pore size distribution of dry postprecipitation thing 2 are preserved to greatest extent, can suppress the generation of particle hard aggregation effectively, obtain the boride particle of specific area height, particle size distribution homogeneous;
5. preparation method of the present invention, the predecessor in the step 3 is heat-treated under the starvation condition, has effectively avoided the generation of oxidation reaction.
6. the boride cost that obtains with preparation method of the present invention is low, can carry out large-scale production in practice; Structure and functional; Form in order to divide equally, shape is identical by loose powder body particle for the boride that obtains, and particle size distribution is narrow, does not have the particle of reuniting between the particle.
Description of drawings
The X-ray spectrum diffraction pattern of the boride that Fig. 1 prepares for embodiment 1.
The X-ray spectrum diffraction pattern of the boride that Fig. 2 prepares for embodiment 2.
The sem photograph of the boride that Fig. 3 prepares for embodiment 2.
The discharge capacity figure of the alkaline battery that Fig. 4 prepares for embodiment 1, wherein abscissa is represented cycle-index, and ordinate is represented discharge capacity, and unit is mAh/g;
Embodiment
Describe the present invention in detail below by specific embodiment:
By following instrument and method the boride that embodiment of the invention 1-9 prepares is detected:
Form through Inductive Coupled Plasma Emission Spectrometer (IRIS/AP, Thermo Jarrell Ash) analytical element, obtain the chemical composition of boride; On NOVA 1200e nitrogen absorption specific surface analyzer, measure the specific area of boride; Carry out pattern with JEOL JSM-6301F ESEM and characterize, can obtain the boride particle size values; Adopt Rigaku DMAX2400 type X-ray diffractometer to characterize the boride structural form.
Embodiment 1
Reactor is placed 4 ℃ of environment, under the magnetic stirrer condition, with 0.1mol/L, the CoCl of 100mL
2Solution adds in the reactor.With the speed of 1mL/min, dropwise drip excessive NaBH again with NaOH adjust pH to 12
4(0.5mol/L 100mL), drip to finish the back and continues to stir 0.5h solution, reacts completely guaranteeing, obtains sediment 1.With suction filtration behind the sediment 1 usefulness deionized water wash of gained three times, obtain sediment 2.Sediment 2 is put into cold-trap, reduce to-90 ℃ with cold-trap, rate of temperature fall is 15 ℃/min, freezing 3h under-90 ℃.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum degree≤10.0Pa (under this experimental technique condition vacuum degree remain on≤10.0Pa gets final product, vacuum degree is constantly to change in the actual experiment process), temperature carries out vacuum treatment 24h under-90 ℃ the condition, obtains presoma.Presoma in Ar atmosphere, with 400 ℃ of calcining 4h, is obtained boride in the tube furnace.Described after testing boride chemical composition is Co
2.01B is boride of the present invention.Fig. 1 is the X-ray spectrum diffraction pattern of embodiment 1 boride, contains a plurality of very narrow " spike " independent of each other among the figure, and characteristic peak wherein is Co
3The diffraction maximum of B, CoB and Co shows that described boride is a crystalline state.Can obtain described boride for dividing equally the loose powder body from sem photograph, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that the specific area of described boride is 36.04m
2/ g, particle diameter are 300nm.
With the boride for preparing and conductive agent Ni powder (boride: the mass ratio of conductive agent Ni powder=1: 3) mix, in mortar, carry out ground and mixed evenly after, obtain mixture.With pack into punching block compressing tablet and be negative plate of described mixture with collector nickel foam coating.Described negative plate and hickelous nydroxide positive plate are separated with barrier film, put into the 100mL electrolyte of 6mol/L KOH+1mol/L LiOH, both positive and negative polarity is drawn by the lug nickel strap respectively, promptly obtains a kind of alkaline battery of the present invention.Described alkaline battery soaks 4h earlier before discharging and recharging experiment in electrolyte, test on LAND CT2001A tester then, and Fig. 4 is the discharge capacity figure of embodiment 1 described a kind of alkaline battery.Discharge capacity reaches 536.8mAh/g under the 100mA/g discharge current density, and has excellent cycle performance, still can reach 438.3mAh/g after 100 weeks.
Embodiment 2
Reactor is placed 4 ℃ of environment, under the magnetic stirrer condition, with 0.1mol/L, the CoCl of 100mL
2Solution adds in the reactor.With the speed of 5mL/min, dropwise drip excessive NaBH again with NaOH adjust pH to 12
4(0.1mol/L 100mL), drip to finish the back and continues to stir 0.5h solution, reacts completely guaranteeing, drives bubble hydrogen away, obtains sediment 1.With suction filtration behind the sediment 1 usefulness deionized water wash of gained three times, obtain sediment 2.Sediment 2 is put into cold-trap, reduce to-90 ℃, freezing 3h under-90 ℃ with cold-trap.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum degree≤10.0Pa (under this experimental technique condition vacuum degree remain on≤10.0Pa gets final product, vacuum degree is constantly to change in the actual experiment process), temperature carries out vacuum treatment 6h under-90 ℃ the condition, obtains presoma.With presoma 50 ℃ of heat treatment 48h under vacuum degree≤10.0Pa condition, obtain boride.Described after testing boride chemical composition is Co
2.05B is boride of the present invention.Fig. 2 is the X-ray spectrum diffraction pattern of embodiment 2 borides, only observes the mild variation of the X ray intensity that is scattered in whole scanning angle scope, and no obvious characteristics peak shows that described boride is an amorphous state.Detect to such an extent that the specific area of described boride is 23.39m
2/ g; Fig. 3 be embodiment 2 described borides sem photograph, can obtain particle diameter is 1 μ m, for dividing equally the loose powder body, promptly particle is formed, shape is identical, particle size distribution is narrow, not have the particle of reunion between the particle.
With the boride for preparing and conductive agent Ni powder (boride: the mass ratio of conductive agent Ni powder=1: 4) mix, in mortar, carry out ground and mixed evenly after, obtain mixture.With pack into punching block compressing tablet and be negative plate of described mixture with collector nickel foam coating.Described negative plate and hickelous nydroxide positive plate are separated with barrier film, put into the 100mL electrolyte of 6mol/L KOH+1mol/L LiOH, both positive and negative polarity is drawn by the lug nickel strap respectively, promptly obtains a kind of alkaline battery of the present invention.Described alkaline battery soaks 4h earlier before discharging and recharging experiment in electrolyte, test on LAND CT2001A tester then, and discharge capacity reaches 430.8mAh/g under the 100mA/g discharge current density, and has excellent cycle performance.
Embodiment 3
Reactor is placed-8 ℃ of environment, under the magnetic stirrer condition, with 0.1mol/L, the CoCl of 100mL
2Solution adds in the reactor.With the speed of 5mL/min, dropwise drip excessive NaBH again with ammoniacal liquor adjust pH to 12
4(0.5mol/L 100mL), drip to finish the back and continues to stir 0.5h solution, reacts completely guaranteeing, drives bubble hydrogen away, obtains sediment 1.With the sediment 1 usefulness absolute ethanol washing of gained 3 times, suction filtration behind the deionized water wash 1 time obtains sediment 2, places 1 hour in-4 ℃ refrigerator.Condenser temperature is reduced to-90 ℃, again the sediment of placing 1 hour in-4 ℃ of refrigerators 2 is put into cold-trap, freezing 6h under-90 ℃.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum degree≤10.0Pa (under this experimental technique condition vacuum degree remain on≤10.0Pa gets final product, vacuum degree is constantly to change in the actual experiment process), temperature carries out vacuum treatment 48h under-90 ℃ the condition, obtains presoma.Presoma is calcined 1h with 500 ℃ in Ar atmosphere tube type stove, obtain boride.Described after testing boride chemical composition is Co
2B is boride of the present invention.In X-ray spectrum diffraction pattern, contain a plurality of very narrow " spike " independent of each other, show that described boride is a crystalline state.Can obtain described boride for dividing equally the loose powder body from sem photograph, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that described boride specific area is 71.4m
2/ g, particle diameter are 100nm.
With the boride for preparing and conductive agent acetylene black (boride: the mass ratio of conductive agent acetylene black=1: 3) mix, in mortar, carry out ground and mixed evenly after, obtain mixture.With pack into punching block compressing tablet and be negative plate of described mixture with collector nickel foam coating.Described negative plate and hickelous nydroxide positive plate are separated with barrier film, put into the 100mL electrolyte of 6mol/L KOH+1mol/L NaOH+0.3mol/L LiOH, both positive and negative polarity is drawn by the lug nickel strap respectively, promptly obtains a kind of alkaline battery of the present invention.Described alkaline battery soaks 4h earlier before discharging and recharging experiment in electrolyte, test on LAND CT2001A tester then, and discharge capacity reaches 441.8mAh/g under the 300mA/g discharge current density, and has excellent cycle performance.
Embodiment 4
Reactor is placed-8 ℃ of environment, under the magnetic stirrer condition, with 0.2mol/L, the CoCl of 100mL
2Solution adds in the reactor.With the speed of 10mL/min, dropwise drip excessive NaBH again with KOH adjust pH to 12
4(1.0mol/L 100mL), drip to finish the back and continues to stir 1h solution, reacts completely guaranteeing, drives bubble hydrogen away, obtains sediment 1.With suction filtration behind the sediment 1 usefulness deionized water wash of gained three times, obtain sediment 2, in-196 ℃ liquid nitrogen, placed 2 hours.Condenser temperature is reduced to-200 ℃, the sediment 2 that will place 2 hours in-196 ℃ of liquid nitrogen is put into the freezing 1h of cold-trap again.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 3, realize dry run.Vacuum degree≤10.0Pa (under this experimental technique condition vacuum degree remain on≤10.0Pa gets final product, vacuum degree is constantly to change in the actual experiment process), temperature carries out vacuum treatment 24h under-200 ℃ the condition, obtains presoma.Presoma is calcined 12h with 300 ℃ under the argon gas atmosphere in tube furnace, obtain boride.Described after testing boride chemical composition is Co
1.85B is boride of the present invention.In X-ray spectrum diffraction pattern, contain a plurality of very narrow " spike " independent of each other, show that described boride is a crystalline state.Can obtain described boride for dividing equally the loose powder body from sem photograph, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that described boride specific area is 198.2m
2/ g, particle diameter are 2nm.
With the boride for preparing and conductive agent Ni powder (boride: the mass ratio of conductive agent Ni powder=1: 3) mix, in mortar, carry out ground and mixed evenly after, obtain mixture.With pack into punching block compressing tablet and be negative plate of described mixture with collector metal nickel screen coating.Described negative plate and hickelous nydroxide positive plate are separated with barrier film, put into the 100mL electrolyte of 6mol/L KOH+2mol/L NaOH, both positive and negative polarity is drawn by the lug aluminium strip respectively, promptly obtains a kind of alkaline battery of the present invention.Described alkaline battery soaks 4h earlier before discharging and recharging experiment in electrolyte, test on LAND CT2001A tester then, and discharge capacity reaches 253.9mAh/g under the 50mA/g discharge current density, and has excellent cycle performance.
Embodiment 5
Under the magnetic stirrer condition, with 0.1mol/L, the CoCl of 100mL
2Solution adds in the reactor.With the speed of 10mL/min, dropwise drip NaBH again with NaOH adjust pH to 14
4(0.5mol/L 100mL), drip to finish the back and continues to stir 0.5h solution, reacts completely guaranteeing, drives bubble hydrogen away, obtains sediment 1.With suction filtration behind the sediment 1 usefulness deionized water wash 5 times, obtain sediment 2.Condenser temperature is reduced to-90 ℃, again sediment 2 is put into cold-trap, freezing 12h under-90 ℃.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum degree≤10.0Pa (under this experimental technique condition vacuum degree remain on≤10.0Pa gets final product, vacuum degree is constantly to change in the actual experiment process), temperature carries out vacuum treatment 12h under-90 ℃ the condition, obtains presoma.Presoma is calcined 36h with 700 ℃ under the argon gas in tube furnace, obtain boride.Described after testing boride chemical composition is Co
1.23B is boride of the present invention.In X-ray spectrum diffraction pattern, contain a plurality of very narrow " spike " independent of each other, show that described boride is a crystalline state.Can obtain described boride for dividing equally the loose powder body from sem photograph, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that described boride specific area is 10.59m
2/ g, particle diameter are 20 μ m.
With the boride for preparing and conductive agent carbon black (boride: the mass ratio of conductive agent carbon black=1: 3) mix, in mortar, carry out ground and mixed evenly after, obtain mixture.With pack into punching block compressing tablet and be negative plate of described mixture with collector carbon cloth coating.Described negative plate and hickelous nydroxide positive plate are separated with barrier film, put into the 100mL electrolyte of 6mol/L KOH+1mol/L NaOH+0.3mol/L LiOH, both positive and negative polarity is drawn by lug nickel aluminium strip respectively, promptly obtains a kind of alkaline battery of the present invention.Described alkaline battery soaks 4h earlier before discharging and recharging experiment in electrolyte, test on LAND CT2001A tester then, and discharge capacity reaches 206.4mAh/g under the 50mA/g discharge current density, and has excellent cycle performance.
Embodiment 6
Under the magnetic stirrer condition, with 0.1mol/L, the CoCl of 100mL
2Solution adds in the reactor.With the speed of 20mL/min, dropwise drip the NaBH of the 0.5mol/L that contains ammoniacal liquor-chloride buffer solution again
4Solution, to the pH value of solution value be 8.Drip to finish the back and continue to stir 0.5h, react completely guaranteeing, drive bubble hydrogen away, obtain sediment 1.With suction filtration behind the sediment 1 usefulness deionized water wash of gained 3 times, obtain sediment 2.Condenser temperature is reduced to-10 ℃, again sediment 2 is put into cold-trap and be cooled to-10 ℃, freezing 12h under-10 ℃.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum degree≤10.0Pa (under this experimental technique condition vacuum degree remain on≤10.0Pa gets final product, vacuum degree is constantly to change in the actual experiment process), temperature carries out vacuum treatment 1h under-10 ℃ the condition, obtains presoma.With presoma in tube furnace under the argon gas atmosphere 850 ℃ the calcining 24h, obtain boride.Described after testing boride chemical composition is Co
2.79B is boride of the present invention.In X-ray spectrum diffraction pattern, contain a plurality of very narrow " spike " independent of each other, show that described boride is a crystalline state.Can obtain described boride for dividing equally the loose powder body from sem photograph, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that described boride specific area is 5.23m
2/ g, particle diameter are 50 μ m.
With the boride for preparing and conductive agent graphite powder (boride: the mass ratio of conductive agent graphite powder=1: 3) mix, in mortar, carry out ground and mixed evenly after, obtain mixture.With pack into punching block compressing tablet and be negative plate of described mixture with collector carbon paper coating.Described negative plate and hickelous nydroxide positive plate are separated with barrier film, put into the 100mL electrolyte of 6mol/L KOH+1mol/L NaOH+0.3mol/L LiOH, both positive and negative polarity is drawn by the lug aluminium strip respectively, promptly obtains a kind of alkaline battery of the present invention.Described alkaline battery soaks 4h earlier before discharging and recharging experiment in electrolyte, test on LAND CT2001A tester then, and discharge capacity reaches 350.4mAh/g under the 50mA/g discharge current density, and has excellent cycle performance.
Embodiment 7
There-necked flask is placed-20 ℃ of environment, under electronics blender stirring condition, with 100 milliliters of CoCl
2And NiCl
2Mixed solution (Co is 1: 1 with the ratio of the amount of substance of Ni) places in the there-necked flask, is 10 5wt%NaBH again with the pH value
4+ 1wt%NaOH solution 100mL dropwise adds in the there-necked flask with 5mL/min speed under the effect of peristaltic pump as reducing agent, fully carries out NaBH in order to ensure reduction reaction
4With the amount of substance ratio of metallic atom be 5: 1.Drip and finish back continuation stirring 0.5h, obtain sediment 1.With suction filtration behind the sediment 1 usefulness deionized water wash of gained 4 times, obtain sediment 2.Condenser temperature is reduced to-80 ℃, again sediment 2 is put into cold-trap freezing 3h under-80 ℃.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum degree≤10.0Pa (under this experimental technique condition vacuum degree remain on≤10.0Pa gets final product, vacuum degree is constantly to change in the actual experiment process), temperature carries out vacuum treatment 24h under-80 ℃ the condition, obtains presoma.With presoma in tube furnace under the argon gas atmosphere 400 ℃ the calcining 4h, obtain boride.Described after testing boride chemical composition is Co
1.05Ni
1.01B is boride of the present invention.In X-ray spectrum diffraction pattern, contain a plurality of very narrow " spike " independent of each other, show that described boride is a crystalline state.Can obtain described boride for dividing equally the loose powder body from sem photograph, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that described boride specific area is 41.06m
2/ g, particle diameter are 200nm.
With the boride for preparing and conductive agent Ni powder (boride: the mass ratio of conductive agent Ni powder=1: 4) mix, in mortar, carry out ground and mixed evenly after, obtain mixture.With pack into punching block compressing tablet and be negative plate of described mixture with collector nickel foil coating.Described negative plate and hickelous nydroxide positive plate are separated with barrier film, put into the 100mL electrolyte of 6mol/L KOH, both positive and negative polarity is drawn by lug nickel aluminium strip respectively, promptly obtains a kind of alkaline battery of the present invention.Described alkaline battery soaks 4h earlier before discharging and recharging experiment in electrolyte, test on LAND CT2001A tester then, and discharge capacity reaches 398.3mAh/g under the 50mA/g discharge current density, and has excellent cycle performance.
Embodiment 8
There-necked flask is placed 0 ℃ of ice bath environment, under the glass bar stirring condition, with 100 milliliters of CoCl
2And MgCl
2Mixed solution (Co is 5: 1 with the ratio of the amount of substance of Mg) places in the there-necked flask, will be 12 100mLNaBH again with sodium carbonate and NaOH accent pH
4Solution dropwise adds in the there-necked flask in order to 7.5mL/min speed at the work of peristaltic pump, drips to finish the back and continue to stir 45min.Obtain sediment 1.With sediment 1 usefulness distilled water washing 3 times, suction filtration behind the absolute ethanol washing 1 time obtains sediment 2.Condenser temperature is reduced to-90 ℃, again sediment 2 is put into cold-trap freezing 3h under-90 ℃.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum degree≤10.0Pa (under this experimental technique condition vacuum degree remain on≤10.0Pa gets final product, vacuum degree is constantly to change in the actual experiment process), temperature carries out vacuum treatment 24h under-90 ℃ the condition, obtains presoma.With presoma N in tube furnace
2With 400 ℃ of calcining 4h, obtain boride under the atmosphere.Described after testing boride chemical composition is Co
2.07Mg
1.89B is boride of the present invention.In X-ray spectrum diffraction pattern, contain a plurality of very narrow " spike " independent of each other, show that described boride is a crystalline state.Can obtain described boride for dividing equally the loose powder body from sem photograph, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that described boride specific area is 47.51m
2/ g, particle diameter are 200nm.
With the boride for preparing and conductive agent Ni powder, conductive agent CoO powder (boride: conductive agent Ni powder: the mass ratio of conductive agent CoO powder=85: 10: 5) mix, in mortar, carry out ground and mixed evenly after, obtain mixture.With pack into punching block compressing tablet and be negative plate of described mixture with collector nickel foam coating.Described negative plate and hickelous nydroxide positive plate are separated with barrier film, put into the 100mL electrolyte of 4mol/L KOH, both positive and negative polarity is drawn by the lug nickel strap respectively, promptly obtains a kind of alkaline battery of the present invention.Described alkaline battery soaks 4h earlier before discharging and recharging experiment in electrolyte, test on LAND CT2001A tester then, and discharge capacity reaches 318mAh/g under the 50mA/g discharge current density, and has excellent cycle performance.
Embodiment 9
Reactor is placed 4 ℃ of environment, under the supersonic oscillations condition, with 0.1mol/L, the FeCl of 100mL
3Solution adds in the reactor.With the speed of 1mL/min, dropwise drip excessive KBH again with saleratus and potassium hydroxide adjust pH to 12
4(0.5mol/L 100mL), drip to finish follow-up persistent oscillation 0.5h to solution, reacts completely guaranteeing, obtains sediment 1.With sediment 1 usefulness deionized water wash 2 times, suction filtration after the acetone washing 1 time obtains sediment 2.Sediment 2 is put into cold-trap, reduce to-90 ℃ with cold-trap, rate of temperature fall is 15 ℃/min.Be incubated 3h down at-90 ℃.Vacuumize behind freezing the finishing, make liquid distillation in the sediment 2, realize dry run.Vacuum degree≤10.0Pa (under this experimental technique condition vacuum degree remain on≤10.0Pa gets final product, vacuum degree is constantly to change in the actual experiment process), temperature carries out vacuum treatment 24h under-90 ℃ the condition, obtains presoma.After the presoma drying, N in tube furnace
2With 500 ℃ of calcining 1h, obtain boride under the atmosphere.Described after testing boride chemical composition is Fe
2B is boride of the present invention.In X-ray spectrum diffraction pattern, contain a plurality of very narrow " spike " independent of each other, show that described boride is a crystalline state.Can obtain described boride for dividing equally the loose powder body from sem photograph, promptly particle is formed, shape is identical, and particle size distribution is narrow, not have the particle of reunion between the particle.Detect to such an extent that described boride specific area is 30.24m
2/ g, particle diameter are 600nm.
With the boride for preparing and conductive agent Ni powder (boride: the mass ratio of conductive agent Ni powder=1: 3) mix, in mortar, carry out ground and mixed evenly after, obtain mixture.With pack into punching block compressing tablet and be negative plate of described mixture with collector nickel foam coating.Described negative plate and hickelous nydroxide positive plate are separated with barrier film, put into the 100mL electrolyte of 2mol/L KOH, both positive and negative polarity is drawn by the lug nickel strap respectively, promptly obtains a kind of alkaline battery of the present invention.Described alkaline battery soaks 4h earlier before discharging and recharging experiment in electrolyte, test on LAND CT2001A tester then, and discharge capacity reaches 312mAh/g under the 30mA/g discharge current density, and has excellent cycle performance.
In sum, more than be preferred embodiment of the present invention only, be not to be used to limit protection scope of the present invention.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. alkaline battery, composition comprises: positive plate, negative plate, barrier film and alkaline electrolyte or polymer dielectric; Wherein, positive plate is for applying or be suppressed with the collector of hickelous nydroxide; By barrier film or polymer dielectric positive/negative plate is separated; Positive plate and negative plate are picked out by lug respectively; It is characterized in that: described negative plate is the collector that is coated with negative material, and negative plate is immersed in the alkaline electrolyte; Described negative material is boride and the mixed uniformly powder of conductive agent;
Wherein, the preparation method of described boride is as follows:
Step 1, the solution that will contain soluble metallic salt add in the reactor, add that excessive to regulate the pH value with alkali or cushioning liquid be 7～14 the BH that contains again
4 -Solution, hybrid reaction obtains sediment 1;
Step 2, with behind sediment 1 usefulness detergent washing 〉=2 time, Separation of Solid and Liquid obtains sediment 2; Then sediment 2 is cooled to below-10 ℃, under vacuum degree≤10.0Pa, carries out vacuum treatment then, obtain predecessor;
Step 3, predecessor is heat-treated under the starvation condition, obtain boride of the present invention;
Wherein, the metallic element in the soluble metallic salt described in the step 1 is one or more among Fe, Ti, Cu, Zn, Al, Zr, Nd, Mo, V, Cr, Co, Ni, Ag or the Mg; Contain BH
4 -Solution in solute be one or more mixture in potassium borohydride, sodium borohydride or the aluminium borohydride; Alkali is one or more the mixture in NaOH, NaOH, lithium hydroxide, ammoniacal liquor, sodium carbonate, sodium acid carbonate, potash, saleratus, calcium hydroxide, barium hydroxide, potassium dihydrogen phosphate or the sodium hydrogen phosphate; Cushioning liquid is a kind of in ammoniacal liquor-chloride buffer solution, borax-calcium chloride cushioning liquid or the borax-sodium carbonate cushioning liquid;
Washing agent in the step 2 is distilled water, deionized water, absolute ethyl alcohol, ethylene glycol, isopropyl alcohol, acetone or methylethylketone; Can wash respectively with identical or different washing agent during washing; Vacuum processing time is 1h～48h;
Heat treatment temperature is 50 ℃～850 ℃ in the step 3, and heat treatment time is 1～48h;
The chemical formula of the boride for preparing with said method is M
xB, wherein M is one or more metallic elements among Fe, Ti, Cu, Zn, Al, Zr, Nd, Mo, V, Cr, Co, Ni, Ag or the Mg, 1≤x≤4, described boride is for all disperseing boride.
2. a kind of alkaline battery according to claim 1 is characterized in that: adding is 7～14 the BH that contains with alkali or cushioning liquid adjusting pH value in the step 1
4 -Solution, be to drip with the speed of 1mL/min～20mL/min; Drip and finish back continuation mixing 0.5h～1h; Mixing condition is that supersonic oscillations, glass bar stir, a kind of in electronic stirring or the magnetic agitation.
3. a kind of alkaline battery according to claim 1 is characterized in that: in the step 1 reactor is placed-20 ℃～4 ℃ environment.
4. a kind of alkaline battery according to claim 1 is characterized in that: the process of in the step 2 sediment 2 being reduced to below-10 ℃ is: sediment 2 is put into cold-trap, be cooled to-10 ℃～-200 ℃ with cold-trap, rate of temperature fall is 5～90 ℃/min; Cooling time is 1h～12h.
5. a kind of alkaline battery according to claim 1, it is characterized in that: the process of in the step 2 sediment 2 being reduced to below-10 ℃ is: condenser temperature is reduced to-10 ℃～-200 ℃, sediment 2 placed 〉=1 hour in the liquid nitrogen of 0 ℃～-20 ℃ refrigerator or-196 ℃～-209 ℃ after, put into the freezing 1h～12h of cold-trap after the cooling.
6. a kind of alkaline battery according to claim 1 is characterized in that: the starvation condition is for charging into inert gas or vacuum degree≤10.0Pa in the step 3; Inert gas is Ar gas or N
2Gas.
7. a kind of alkaline battery according to claim 1 is characterized in that: the structural form of described boride is crystalline state or amorphous state.
8. a kind of alkaline battery according to claim 1 is characterized in that: the particle diameter of described boride is 2nm～50 μ m; The specific area of described boride is 5m
2/ g～200m
2/ g.
9. a kind of alkaline battery according to claim 1 is characterized in that: described lug is a kind of in nickel strap, aluminium strip or the nickel aluminium strip; Described conductive agent is one or more the mixture in metal powder, metal oxide, alloyed powder, carbonaceous mesophase spherules, acetylene black, graphite, carbon nano-tube or the Graphene; Described collector is a kind of in nickel foam, wire netting, metal forming, carbon cloth or the carbon paper; The solvent of described alkaline electrolyte is a water, and solute is one or more the mixture among KOH, NaOH or the LiOH, and concentration is 2-8mol/L.
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