CN107492633A - A kind of Raney Ni/NiCl2Composite positive pole and preparation method thereof - Google Patents

A kind of Raney Ni/NiCl2Composite positive pole and preparation method thereof Download PDF

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Publication number
CN107492633A
CN107492633A CN201710537369.XA CN201710537369A CN107492633A CN 107492633 A CN107492633 A CN 107492633A CN 201710537369 A CN201710537369 A CN 201710537369A CN 107492633 A CN107492633 A CN 107492633A
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raney
nicl
positive pole
composite positive
preparation
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CN107492633B (en
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罗重霄
刘凯特
汤胜
胡华荣
叶丹宏
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Shanghai Institute of Space Power Sources
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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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/582—Halogenides
    • 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
    • H01M4/626—Metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/30—Deferred-action cells
    • H01M6/36—Deferred-action cells containing electrolyte and made operational by physical means, e.g. thermal cells

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Inert Electrodes (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides Raney Ni/NiCl2Composite positive pole and preparation method thereof, Raney Ni/NiCl provided by the invention2Composite positive pole preparation method includes：Step 1: weighing Raney Ni, it is placed in after replacing water and washing with absolute ethyl alcohol in the container for filling deionized water；Step 2: at a temperature of 40 80 DEG C, NaClO and surfactant, stirring are added into beaker；Washed after suction filtration with absolute ethyl alcohol and deionized water, place into and predecessor is dried to obtain in vacuum drying chamber；Step 3: by predecessor and NH4Muffle kiln roasting is placed in after Cl ground and mixeds, naturally cools to room temperature, Raney Ni/NiCl will be obtained after block product ball mill grinding2Composite positive pole.Raney Ni/NiCl prepared by the present invention2Composite positive pole specific surface area is big, and resistivity is small.

Description

A kind of Raney Ni/NiCl2Composite positive pole and preparation method thereof
Technical field
The present invention relates to technical field of material chemistry, and in particular to a kind of Raney Ni/NiCl2Composite positive pole and its preparation Method.
Background technology
Thermal cell be with battery heating system in itself the heating melting of nonconducting solid state salt electrolyte be in from Reserve cell of subtype conductor and entrance working condition.Long-term storage, the high and quick activation of specific power are its main spies Point, it is significant in military field particularly suitable as various guided missiles and the supporting power supply of armament systems.So far, FeS2And CoS2Be using lithium based material as the thermal cell of negative pole in two kinds of researchs it is most widely used, the most ripe positive electrode of technology, But the floating voltage of monomer only has 1.9-2.0V or so, is unfavorable for the further lifting of thermal cell specific power.
NiCl2Belong to high potential compound, when being used cooperatively with lithium alloy negative pole, monomer zero load maximum voltage exceedes 2.5V, this is that other cathode materials are unable to reach, and is particularly suitable for the use of power output type thermal cell.Accordingly, with respect to NiCl2Make Increasing concern both at home and abroad is received for hot high pressure positive electrode for battery material.But regrettably, do not have still in world wide Ripe thermal cell type product really selects NiCl2Use, trace it to its cause 2 points nothing more than as positive electrode：1)NiCl2 The close structure before high temperature distillation processing is not carried out, specific surface area is low, and electro-chemical activity is very poor, and high temperature distillation equipment cost High and steam corrosion is strong, it is difficult to produces in enormous quantities；2)NiCl2Resistivity it is high, activation initial voltage platform has significantly Pit is present, and has a strong impact on the normal work of load on bullet.
At present, on NiCl2The preparation of positive electrode and study on the modification are a lot, as Chu Ying et al. proposes a kind of liter China-reduction prepares NiCl2Method (Journal of Inorganic Materials, 2016,31 (9) of-Ni composite positive poles：992-996), electric conductivity Preferably, tentatively solve the problems, such as that thermal cell activates initial voltage platform pit, but this method still needs high temperature sublimation apparatus, Do not possess actual production and the possibility applied.Guo Yong congruences people prepares NiCl using high temperature distillation method2Powder, add conducting powder With electrolyte powder is last obtains NiCl2Positive electrode (Chinese patent, CN102157722A), but this method is also required to high temperature distillation Equipment, and yield is very low, does not possess actual production and the possibility applied equally.Xiao Zhi summers et al. use first principle pair NiCl2The growth of crystal is simulated, and is prepared for anhydrous NiCl using direct drying method2Crystal (institution of higher education's Science of Chemistry Report, 2015,36 (12)：2497-2503), the NiCl that the method obtains2Crystal surface structure is closely knit, and electro-chemical activity is poor, it is difficult to Used as thermal cell positive electrode.Li Jin brightness et al. prepares NiCl using chlorinating roasting from battery waste2, so as to obtain Extract effect (Hydrometallurgy, 2009,99 (1-2) of metallic nickel:7-12), but the starting point of this method is chlorination smelting Gold extraction metallic nickel, and technological process is complicated, the NiCl prepared2Purity can not meet the requirement of thermal cell.
The content of the invention
The present invention solves the problems, such as it is existing NiCl2Material is used for that anode specific surface area to be low, resistivity is high；It is unresolved Described problem, the present invention provide a kind of Raney Ni/NiCl2Composite positive pole and preparation method thereof.
Raney Ni/NiCl provided by the invention2Composite positive pole includes：NiCl2With Raney Ni, NiCl2Quality Percentage amounts are 8-34%, and Raney Ni quality percentage amounts are 66-92%.
The Raney Ni/NiCl that the present invention also provides2The preparation method of composite positive pole, including：
Step 1: weighing Raney Ni, it is placed in after replacing water and washing with absolute ethyl alcohol in the container for filling deionized water；
Step 2: at a temperature of 40-80 DEG C, it is Raney Ni gross masses 5-20%'s that quality is added into beaker NaClO, then the surfactant that quality is Raney Ni gross masses 0-5% is added into beaker, 2-6h is stirred, nothing is used after suction filtration Water-ethanol and deionized water washing, place into and predecessor are dried to obtain in vacuum drying chamber；
Step 3: by predecessor and NH4It is placed in Muffle furnace after Cl ground and mixeds, is calcined under conditions of 300-600 DEG C 0.5-2h, room temperature is naturally cooled to, Raney Ni/NiCl will be obtained after block product ball mill grinding2Composite positive pole； NH4Cl mass is 0.5-4 times of predecessor gross mass.
Further, vacuum drying chamber vacuum is not more than -0.08MPa in the step 2, and temperature is 95 DEG C.
Further, described surfactant is nonionic surfactant, nonionic surfactant be aliphatic alcohols, Polyethylene glycols, polyvinyl alcohol, alkylolamides class, alkyl amine or its mixture.
Further, NaClO mass is the 6-10% of Raney Ni gross masses in the step 2.
Further, NH in the step 34Cl mass is 1.0-2.0 times of predecessor quality.
Further, the step 3 Muffle furnace sintering temperature is 400-500 DEG C, roasting time 1-1.5h.
Advantages of the present invention includes：For existing NiCl2The deficiency of positive electrode and preparation method, creative proposes One kind uses Raney Ni catalyst to prepare Raney Ni/NiCl for raw material2The method of composite positive pole, this is compound just Pole material inherits the big outstanding feature of Raney Ni raw material specific surface areas, and electro-chemical activity is been significantly enhanced, and material The presence of middle metallic nickel compensate for single NiCl2The shortcomings that material electronics electrical conductivity deficiency, in addition preparation side provided by the invention Method also has without bazardous waste discharge, technical process is simple, without high temperature sublimation apparatus, low power consumption and other advantages, possesses The potentiality really applied in thermal cell type product.
Embodiment
Hereinafter, spirit and substance of the present invention are further elaborated in conjunction with the embodiments.
Hereinafter, by embodiment, the present invention is further elaborated.
Embodiment 1
According to target product Raney Ni/NiCl2The Raney that Ni elements total weight in composite positive pole needs Ni weight.The commercially available Raney Ni catalyst of 100g is weighed in the present embodiment, water is replaced with absolute ethyl alcohol and washs, then will Raney Ni are transferred into the beaker for filling deionized water.80 DEG C are warming up to, adds 20g NaClO and 5g polyethylene glycol 400s, is delayed Slow stirring 6h, filters and is put into after wash with absolute ethyl alcohol and deionized water in vacuum drying chamber, be not more than in vacuum- Dried in the environment of 0.08MPa and 95 DEG C, obtain about 105g predecessors.Again by predecessor and 420g NH4Cl ground and mixeds are uniform And load quartzy bowl, then be transferred in Muffle furnace, 2h is calcined under conditions of 600 DEG C, naturally cools to room temperature, by block product ball Be milled broken rear i.e. acquisition Raney Ni/NiCl2Composite positive pole.
Product is detected using ICP-AES, wherein NiCl2Content be 34%, surplus is Raney Ni；Nitrogen physical absorption is examined Survey result and show that product specific surface area is 42m2·g-1；Resistivity testing product resistance is 0.098 Ω cm.
Embodiment 2
According to target product Raney Ni/NiCl2Ni element gross weights in composite positive pole, it is commercially available to weigh 100g Raney Ni catalyst, replace water with absolute ethyl alcohol and wash, then Raney Ni are transferred to the beaker for filling deionized water In.40 DEG C are warming up to, adds 5g NaClO, is slowly stirred 2h, filters and is put into after being washed with absolute ethyl alcohol and deionized water true In empty drying box, dried in the environment of vacuum is not more than -0.08MPa and 95 DEG C, obtain about 102.6g predecessors.Again by before Drive thing and 51.3g NH4Cl ground and mixeds are uniform and load quartzy bowl, then are transferred in Muffle furnace, are calcined under conditions of 300 DEG C 0.5h, room temperature is naturally cooled to, Raney Ni/NiCl will be obtained after block product ball mill grinding2Composite positive pole.
Product is detected using ICP-AES, wherein NiCl2Content be 8%, surplus is Raney Ni；Nitrogen physical absorption is examined Survey result and show that product specific surface area is 65m2·g-1；Resistivity testing product resistance is 0.072 Ω cm.
Embodiment 3
According to target product Raney Ni/NiCl2Ni element gross weights in composite positive pole, it is commercially available to weigh 100g Raney Ni catalyst, replace water with absolute ethyl alcohol and wash, then Raney Ni are transferred to the beaker for filling deionized water In.Be warming up to 60 DEG C, add 10g NaClO and 3g triton x-100s, be slowly stirred 4h, filter and with absolute ethyl alcohol and go from It is put into after sub- water washing in vacuum drying chamber, dries, obtained about in the environment of vacuum is not more than -0.08MPa and 95 DEG C 103g predecessors.Again by predecessor and 206g NH4Cl ground and mixeds are uniform and load quartzy bowl, then are transferred in Muffle furnace, 2.0h is calcined under conditions of 450 DEG C, naturally cools to room temperature, Raney Ni/NiCl will be obtained after block product ball mill grinding2 Composite positive pole.
Product is detected using ICP-AES, wherein NiCl2Content be 22%, surplus is Raney Ni；Nitrogen physical absorption is examined Survey result and show that product specific surface area is 57m2·g-1；Resistivity testing product resistance is 0.081 Ω cm.
Embodiment 4
According to target product Raney Ni/NiCl2Ni element gross weights in composite positive pole, it is commercially available to weigh 100g Raney Ni catalyst, replace water with absolute ethyl alcohol and wash, then Raney Ni are transferred to the beaker for filling deionized water In.It is warming up to 60 DEG C, adds 6g NaClO and 5g triton x-100s, be slowly stirred 4h, filters and with absolute ethyl alcohol and deionization It is put into after water washing in vacuum drying chamber, is dried in the environment of vacuum is not more than -0.08MPa and 95 DEG C, obtain about 103g Predecessor.Again by predecessor and 206g NH4Cl ground and mixeds are uniform and load quartzy bowl, then are transferred in Muffle furnace, at 400 DEG C Under conditions of be calcined 1.5h, naturally cool to room temperature, will be to obtain Raney Ni/NiCl after block product ball mill grinding2It is compound Positive electrode.
Product is detected using ICP-AES, wherein NiCl2Content be 20%, surplus is Raney Ni；Nitrogen physical absorption is examined Survey result and show that product specific surface area is 77m2·g-1；Resistivity testing product resistance is 0.08 Ω cm.
Embodiment 5
According to target product Raney Ni/NiCl2Ni element gross weights in composite positive pole, it is commercially available to weigh 100g Raney Ni catalyst, replace water with absolute ethyl alcohol and wash, then Raney Ni are transferred to the beaker for filling deionized water In.It is warming up to 60 DEG C, adds 10g NaClO and 3g polyvinyl alcohol, be slowly stirred 4h, filters and with absolute ethyl alcohol and deionized water It is put into vacuum drying chamber, is dried in the environment of vacuum is not more than -0.08MPa and 95 DEG C, before obtaining about 104g after washing Drive thing.Again by predecessor and 104g NH4Cl ground and mixeds are uniform and load quartzy bowl, then are transferred in Muffle furnace, at 500 DEG C Under the conditions of be calcined 1.0h, naturally cool to room temperature, will be to obtain Raney Ni/NiCl after block product ball mill grinding2It is compound just Pole material.
Product is detected using ICP-AES, wherein NiCl2Content be 32%, surplus is Raney Ni；Nitrogen physical absorption is examined Survey result and show that product specific surface area is 70m2·g-1；Resistivity testing product resistance is 0.091 Ω cm.
To sum up, the present invention synthesizes the Raney Ni/NiCl that a kind of suitable high pressure thermal cell uses first2Anode composite material Material, the composite positive pole main design idea are to generate knot in the commercially available Raney Ni catalyst surfaces with bigger serface The loose NiCl of structure2, breakthrough solves common NiCl2It is difficult to obtain in thermal cell because of resistivity height, electric discharge poor activity Really the drawbacks of application.
Further, the present invention proposes NaClO oxidations-NH4The preparation method that Cl chlorinations are combined, can be by changing NaClO Oxidant and NH4The dosage of Cl chlorinating agents, controllableization of target product composition and structure is realized, possess resistivity, compare table The flexible modulation ability of the performance such as area and electro-chemical activity, performance of the different thermal cell type products to positive electrode can be met It is required that have wide range of applications.
3rd, in preparation process, the discharge of no bazardous waste, technological process is simple, particularly without high temperature Sublimation apparatus, its large-scale industrial production is set to become possibility, great military significance and economic value.
Although the present invention is disclosed as above with preferred embodiment, it is not for limiting the present invention, any this area Technical staff without departing from the spirit and scope of the present invention, may be by the methods and technical content of the disclosure above to this hair Bright technical scheme makes possible variation and modification, therefore, every content without departing from technical solution of the present invention, according to the present invention Any simple modifications, equivalents, and modifications made to above example of technical spirit, belong to technical solution of the present invention Protection domain.

Claims (7)

  1. A kind of 1. Raney Ni/NiCl2Composite positive pole, it is characterised in that including：NiCl2With Raney Ni, NiCl2Matter Amount percentage amounts are 8-34%, and Raney Ni quality percentage amounts are 66-92%.
  2. 2. the Raney Ni/NiCl described in claim 12The preparation method of composite positive pole, it is characterised in that including：
    Step 1: weighing Raney Ni, it is placed in after replacing water and washing with absolute ethyl alcohol in the container for filling deionized water；
    Step 2: at a temperature of 40-80 DEG C, the NaClO that quality is Raney Ni gross masses 5-20% is added into beaker, then The surfactant that quality is Raney Ni gross masses 0-5% is added into beaker, stirs 2-6h, after suction filtration with absolute ethyl alcohol and Deionized water is washed, and places into and predecessor is dried to obtain in vacuum drying chamber；
    Step 3: by predecessor and NH4It is placed in after Cl ground and mixeds in Muffle furnace, 0.5- is calcined under conditions of 300-600 DEG C 2h, room temperature is naturally cooled to, Raney Ni/NiCl will be obtained after block product ball mill grinding2Composite positive pole；NH4Cl matter Measure as 0.5-4 times of predecessor gross mass.
  3. 3. according to the Raney Ni/NiCl described in claim 22The preparation method of composite positive pole, it is characterised in that described Vacuum drying chamber vacuum is not more than -0.08MPa in step 2, and temperature is 95 DEG C.
  4. 4. according to the Raney Ni/NiCl described in claim 22The preparation method of composite positive pole, it is characterised in that described Surfactant be nonionic surfactant, nonionic surfactant is aliphatic alcohols, polyethylene glycols, polyvinyl alcohol Class, alkylolamides class, alkyl amine or its mixture.
  5. 5. according to the Raney Ni/NiCl described in claim 22The preparation method of composite positive pole, it is characterised in that described NaClO mass is the 6-10% of Raney Ni gross masses in step 2.
  6. 6. according to the Raney Ni/NiCl described in claim 22The preparation method of composite positive pole, it is characterised in that described NH in step 34Cl mass is 1.0-2.0 times of predecessor quality.
  7. 7. according to the Raney Ni/NiCl described in claim 22The preparation method of composite positive pole, it is characterised in that described Step 3 Muffle furnace sintering temperature is 400-500 DEG C, roasting time 1-1.5h.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1565731A (en) * 2003-06-13 2005-01-19 上海师范大学 Method for preparing novel Raney Ni catalyzer and its application
CN102148352A (en) * 2010-02-10 2011-08-10 上海空间电源研究所 Novel composite anode material for thermal battery and preparation method thereof
CN102157722A (en) * 2011-03-21 2011-08-17 中国电子科技集团公司第十八研究所 Preparation method of positive pole material of thermal battery
CN104894595A (en) * 2015-05-19 2015-09-09 派新（上海）能源技术有限公司 High-catalytic-activity amorphous metal oxide hydrogen evolution electrode and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1565731A (en) * 2003-06-13 2005-01-19 上海师范大学 Method for preparing novel Raney Ni catalyzer and its application
CN102148352A (en) * 2010-02-10 2011-08-10 上海空间电源研究所 Novel composite anode material for thermal battery and preparation method thereof
CN102157722A (en) * 2011-03-21 2011-08-17 中国电子科技集团公司第十八研究所 Preparation method of positive pole material of thermal battery
CN104894595A (en) * 2015-05-19 2015-09-09 派新（上海）能源技术有限公司 High-catalytic-activity amorphous metal oxide hydrogen evolution electrode and preparation method thereof

Non-Patent Citations (2)

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Title
J. BALEJ等: "Preparation and properties of Raney nickel electrodes on Ni-Zn base for H2 and O2 evolution from alkaline solutions Part II", 《JOURNAL OF APPLIED ELECTROCHEMISTRY》 *
褚颖 等: "高导电性热电池正极材料Ni-NiCl2复合物的原位合成与放电性能研究", 《无机化学学报》 *

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