CN104201347A - Method for assisted synthesis of nano-nickel sulfur compounds by sulfur-containing biological amino acids - Google Patents

Method for assisted synthesis of nano-nickel sulfur compounds by sulfur-containing biological amino acids Download PDF

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Publication number
CN104201347A
CN104201347A CN201410478498.2A CN201410478498A CN104201347A CN 104201347 A CN104201347 A CN 104201347A CN 201410478498 A CN201410478498 A CN 201410478498A CN 104201347 A CN104201347 A CN 104201347A
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sulfur
nickel
nano
biological amino
amino acids
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孙俊才
刘玲娟
李嵩
文钟晟
季世军
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Dalian Maritime University
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Dalian Maritime University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/11—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention relates to a method for assisted synthesis of nano-nickel sulfur compounds by sulfur-containing biological amino acids, and belongs to the technical field of lithium ion batteries. The method takes the sulfur-containing biological amino acids as raw materials and adopts a wet chemical method to synthesize the nano-nickel sulfur compounds. The sulfur-containing biological amino acids comprise L-cysteine, L-cystine or glutathione or methionine. The method for the assisted synthesis of the nano-nickel sulfur compounds by the sulfur-containing biological amino acids has the benefits of taking easily obtained sulfur-containing biological amino acids as the raw materials, and utilizing interactions of molecular structures and special functional groups of the sulfur-containing biological amino acids such as -SN and -NH3 to prepare the nano-nickel sulfur compounds of different morphologies and atomic ratios.

Description

The method of the auxiliary synthesis of nano nickel sulphur compound of a kind of sulfur-bearing biological amino acid
Technical field
The method that the present invention relates to the auxiliary synthesis of nano nickel sulphur compound of a kind of sulfur-bearing biological amino acid, belongs to technical field of lithium ion.
Background technology
As important secondary cell, meritorious compensation and the field such as adjustmenting management, electric automobile at energy storage, intelligent grid and the microgrid of portable power source, regenerative resource power transmission and transformation has a wide range of applications lithium ion battery.The performance of active substance of lithium ion battery anode is directly determining the capacity of lithium ion battery.Electrochemical specific capacity for anode material for lithium-ion batteries is all less than 300mAh/g at present.Development and the anode material for lithium-ion batteries of seeking height ratio capacity are the important channels of improving capacity of lithium ion battery.Nano nickel sulphur compound is the anode material for lithium-ion batteries of the important height ratio capacity of a class.
Nano material because size is little, specific surface is large and the reason such as quantum size effect, there are the new features that are different from conventional solid, be widely used in a lot of fields, mainly comprise nanometer luminescent material, nano magnetic material, new ceramics, nanosensor material, nano electrochemical material and nanometer robot etc.Transient metal sulfide has special electronic structure, molecular structure and electromagnetic property as a kind of important inorganic functional material, also there is unique one-tenth key mode, in fields such as resonance image-forming, superconductor, space technology, particle accelerator, geophysical explorations, be widely used simultaneously.NiS in nickel metal sulfide is a kind of semiconductor nano material of function admirable, in solar cell and hydrodesulfurization catalytic reaction, be widely used, aspect anode material of lithium battery, have very large application potential, its theoretical electrochemistry capacity reaches 590mAh/g.Ni in nickel metal sulfide 3s 4the advantages such as the electrochemistry capacitance high (C=704.5mAh/g) with theoretical removal lithium embedded, storage lithium ability is strong, chemical stability is good are a kind of desirable anode material for lithium-ion batteries.NiS in nickel metal sulfide 2also there is good storage lithium ability.
The nickel sulphur compound nano material that people have synthesized different morphologies in succession at present.Main method has wet chemistry method, solid state reaction and physical vaporous deposition etc.CN1974415A discloses and a kind of carbochain is dissolved in and in ionic liquid, prepares bar-shaped NiS[and open the bright fourth of the twelve Earthly Branches, Zhang Chunli, etc. the preparation method of nanometer nickel sulfide rod [P] .CN1974415A, 2007.06.06] method.CN102633309A disclose a kind of by nickel salt, sulphur source, complexing agent with certain mixed in molar ratio, Hydrothermal Synthesis the NiS of cube shaped, spherical and sheet shape 2[Cao Xiaohui, Meng Jinhong, etc. the controlled NiS of a kind of pattern 2hydrothermal preparing process [P] .CN102633309A, 2012.08.15] method, Geng Xinling is with NiSO 46H 2o and Na 2s 2o 42H 2o is raw material, adopts liquid phase method room temperature to synthesize Ni 3s 4[Geng Xinling, Yuan Wei. Liquid preparation methods Ni 3s 4nano powder [J]. Journal of Inorganic Materials, 2003,18 (01): 149-155] method.But in said method, the sulphur source of employing is inorganic compound, produces a large amount of hydrogen sulfide gas in course of reaction, has the potential hazard of environmental pollution.
Summary of the invention
The present invention replaces inorganic sulfur of the prior art source as structure directing agent and sulphur source by sulfur-bearing biological amino acid, the nano nickel sulphur compound that adopts the synthetic different-shape of wet chemistry method, has solved the problem that produces a large amount of hydrogen sulfide gas contaminated environment in above-mentioned course of reaction.
The method that the invention provides the auxiliary synthesis of nano nickel sulphur compound of a kind of sulfur-bearing biological amino acid, described method be take sulfur-bearing biological amino acid as raw material, adopts wet chemistry method synthesis of nano nickel sulphur compound;
Described sulfur-bearing biological amino acid is Cys, CYSTINE, glutathione or methionine.
Sulfur-bearing biological amino acid initial concentration of the present invention is preferably 0.03～0.20mol/L.
The method of the invention is preferably and nickel source is dissolved in to solvent obtains solution I, sulfur-bearing biological amino acid is dissolved in to solvent and obtains solution II, solution I and solution II are mixed, and adjust pH to 1～12,160～260 ℃ of reaction 12～48h, washing, dry.
Nickel of the present invention source is preferably nickel acetate, nickel chloride or nickelous sulfate.
Solvent of the present invention is preferably water or absolute ethyl alcohol.
Nickle atom in nickel of the present invention source and sulfur-bearing biological amino acid and the mol ratio of sulphur atom are preferably 1:1～5.
The nano nickel sulphur compound that the present invention is synthetic be NiS, NiS mutually 2and Ni 3s 4in at least one, the diameter that its pattern is nanocrystalline composition is nanosphere, nanometer lamination flower or the nano flower of 0.5～15 μ m.
Beneficial effect of the present invention is:
1. to take the sulfur-bearing biological amino acid being easy to get be raw material in the present invention, utilizes its molecular structure and specific functional groups, as the nano nickel sulphur compound of different-shape and different atomic ratios is prepared in-the interaction of SH ,-NH3 etc.;
2. synthetic method raw material availability of the present invention is high, simple to operate, production cost is low, advantages of environment protection.
Accompanying drawing explanation
Accompanying drawing 3 width of the present invention,
Fig. 1 is the spherical NiS of the synthetic nanometer of embodiment 3 2xRD figure;
Fig. 2 is the spherical Ni of the synthetic nanometer of embodiment 4 3s 4xRD figure;
Fig. 3 is the SEM figure of the synthetic nano flower-like NiS of embodiment 6.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Test method described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1
The method of the auxiliary synthesis of nano nickel sulphur compound of a kind of Cys, described method is is that 1:1 gets nickel acetate and Cys by the mol ratio of nickle atom and sulphur atom, nickel acetate is dissolved in to 40mL absolute ethyl alcohol and obtains nickel acetate ethanolic solution, Cys is dissolved in to 40mL absolute ethyl alcohol and obtains Cys ethanolic solution, nickel acetate ethanolic solution and Cys ethanolic solution are mixed and obtain the mixed solution that Cys initial concentration is 0.18mol/L, with concentrated ammonia liquor adjust pH to 7, join 200 ℃ of reaction 24h in 100mL teflon-lined autoclave, naturally cool to room temperature, use respectively deionized water and absolute ethyl alcohol centrifuge washing each 3 times, 60 ℃ of dry 12h, obtain NiS black powder.
Embodiment 2
The method of the auxiliary synthesis of nano nickel sulphur compound of a kind of Cys, described method is is that 1:1 gets nickel acetate and Cys by the mol ratio of nickle atom and sulphur atom, nickel acetate is dissolved in to 40mL deionized water and obtains nickel acetate aqueous solution, Cys is dissolved in to 40mL deionized water and obtains the Cys aqueous solution, nickel acetate aqueous solution and the Cys aqueous solution are mixed and obtains the mixed solution that Cys initial concentration is 0.07mol/L, with concentrated ammonia liquor adjust pH to 7, join 160 ℃ of reaction 48h in 100mL teflon-lined autoclave, naturally cool to room temperature, use respectively deionized water and absolute ethyl alcohol centrifuge washing each 3 times, 60 ℃ of dry 12h, obtain NiS and Ni 3s 4mixture.
Embodiment 3
The method of the auxiliary synthesis of nano nickel sulphur compound of a kind of Cys, described method is is that 1:2 gets nickel acetate and Cys by the mol ratio of nickle atom and sulphur atom, nickel acetate is dissolved in to 40mL deionized water and obtains nickel acetate aqueous solution, Cys is dissolved in to 40mL deionized water and obtains the Cys aqueous solution, nickel acetate aqueous solution and the Cys aqueous solution are mixed and obtains the mixed solution that Cys initial concentration is 0.03mol/L, with concentrated ammonia liquor adjust pH to 7, join 260 ℃ of reaction 12h in 100mL teflon-lined autoclave, naturally cool to room temperature, use respectively deionized water and absolute ethyl alcohol centrifuge washing each 3 times, 60 ℃ of dry 12h, obtain NiS 2black powder, its pattern is the nanosphere of diameter 2～3 μ m.
Embodiment 4
The method of the auxiliary synthesis of nano nickel sulphur compound of a kind of Cys, described method is is that 1:3 gets nickel acetate and Cys by the mol ratio of nickle atom and sulphur atom, nickel acetate is dissolved in to 40mL deionized water and obtains nickel acetate aqueous solution, Cys is dissolved in to 40mL deionized water and obtains the Cys aqueous solution, nickel acetate aqueous solution and the Cys aqueous solution are mixed and obtains the mixed solution that Cys initial concentration is 0.10mol/L, with concentrated hydrochloric acid adjust pH to 1, join 180 ℃ of reaction 40h in 100mL teflon-lined autoclave, naturally cool to room temperature, use respectively deionized water and absolute ethyl alcohol centrifuge washing each 3 times, 60 ℃ of dry 12h, obtain Ni 3s 4powder, its pattern is the nanosphere of diameter 8～15 μ m, there is flower-shaped little nanometer group on surface.
Embodiment 5
The method of the auxiliary synthesis of nano nickel sulphur compound of a kind of CYSTINE, described method is is that 1:3 gets nickel acetate and CYSTINE by the mol ratio of nickle atom and sulphur atom, nickel acetate is dissolved in to 40mL deionized water and obtains nickel acetate aqueous solution, CYSTINE is dissolved in to 40mL deionized water and obtains the CYSTINE aqueous solution, nickel acetate aqueous solution and the CYSTINE aqueous solution are mixed and obtains the mixed solution that CYSTINE initial concentration is 0.08mol/L, with concentrated hydrochloric acid adjust pH to 3, join 240 ℃ of reaction 32h in 100mL teflon-lined autoclave, naturally cool to room temperature, use respectively deionized water and absolute ethyl alcohol centrifuge washing each 3 times, 60 ℃ of dry 12h, obtain NiS 2powder, its pattern is the nanosphere of diameter 0.5～4 μ m.
Embodiment 6
The method of the auxiliary synthesis of nano nickel sulphur compound of a kind of glutathione, described method is is that 1:4 gets nickel acetate and glutathione by the mol ratio of nickle atom and sulphur atom, nickel acetate is dissolved in to 40mL deionized water and obtains nickel acetate aqueous solution, glutathione is dissolved in to 40mL deionized water and obtains the glutathione aqueous solution, nickel acetate aqueous solution and the glutathione aqueous solution are mixed and obtains the mixed solution that glutathione initial concentration is 0.07mol/L, with concentrated ammonia liquor adjust pH to 10, join 200 ℃ of reaction 20h in 100mL teflon-lined autoclave, naturally cool to room temperature, use respectively deionized water and absolute ethyl alcohol centrifuge washing each 3 times, 60 ℃ of dry 12h, obtain NiS powder, its pattern is the nano flower of diameter 3～8 μ m.
Embodiment 7
The method of the auxiliary synthesis of nano nickel sulphur compound of a kind of Cys, described method is is that 1:5 gets nickel acetate and Cys by the mol ratio of nickle atom and sulphur atom, nickel acetate is dissolved in to 40mL deionized water and obtains nickel acetate aqueous solution, Cys is dissolved in to 40mL deionized water and obtains the Cys aqueous solution, nickel acetate aqueous solution and the Cys aqueous solution are mixed and obtains the mixed solution that Cys initial concentration is 0.09mol/L, with concentrated ammonia liquor adjust pH to 12, join 220 ℃ of reaction 16h in 100mL teflon-lined autoclave, naturally cool to room temperature, use respectively deionized water and absolute ethyl alcohol centrifuge washing each 3 times, 60 ℃ of dry 12h, obtain NiS powder, its pattern is the nanometer lamination flower of diameter 2～12 μ m.
Embodiment 8
The method of the auxiliary synthesis of nano nickel sulphur compound of a kind of methionine, described method is is that 1:4 gets nickel chloride and methionine by the mol ratio of nickle atom and sulphur atom, nickel chloride is dissolved in to 40mL deionized water and obtains nickel chloride aqueous solution, methionine is dissolved in to 40mL deionized water and obtains the methionine aqueous solution, nickel chloride aqueous solution and the methionine aqueous solution are mixed and obtains the mixed solution that methionine initial concentration is 0.08mol/L, with concentrated ammonia liquor adjust pH to 9, join 220 ℃ of reaction 18h in 100mL teflon-lined autoclave, naturally cool to room temperature, use respectively deionized water and absolute ethyl alcohol centrifuge washing each 3 times, 60 ℃ of dry 12h, obtain NiS 2powder, its pattern is the nanosphere of diameter 4～8 μ m.

Claims (6)

1. a method for the auxiliary synthesis of nano nickel sulphur compound of sulfur-bearing biological amino acid, is characterized in that: described method be take sulfur-bearing biological amino acid as raw material, adopts wet chemistry method synthesis of nano nickel sulphur compound;
Described sulfur-bearing biological amino acid is Cys, CYSTINE, glutathione or methionine.
2. method according to claim 1, is characterized in that: described sulfur-bearing biological amino acid initial concentration is 0.03～0.20mol/L.
3. method according to claim 2, is characterized in that: described method obtains solution I for nickel source is dissolved in to solvent, sulfur-bearing biological amino acid is dissolved in to solvent and obtains solution II, solution I and solution II are mixed to adjust pH to 1～12,160～260 ℃ of reaction 12～48h, washing, dry.
4. method according to claim 3, is characterized in that: described nickel source is nickel acetate, nickel chloride or nickelous sulfate.
5. method according to claim 3, is characterized in that: described solvent is water or absolute ethyl alcohol.
6. method according to claim 3, is characterized in that: the nickle atom in described nickel source and sulfur-bearing biological amino acid and the mol ratio of sulphur atom are 1:1～5.
CN201410478498.2A 2014-09-18 2014-09-18 Method for assisted synthesis of nano-nickel sulfur compounds by sulfur-containing biological amino acids Pending CN104201347A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108133967A (en) * 2017-11-14 2018-06-08 吉林大学 A kind of ultra-violet (UV) band part reflective semitransparent film and preparation method thereof
CN108597893A (en) * 2018-05-28 2018-09-28 江苏大学 A kind of preparation method based on the composite electrode material for super capacitor in nickel foam

Citations (3)

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US20130295469A1 (en) * 2012-05-03 2013-11-07 Ut-Battelle, Llc Lithium sulfide compositions for battery electrolyte and battery electrode coatings
CN103872323A (en) * 2014-03-19 2014-06-18 上海交通大学 Preparation method of nano transition metal sulfide material of positive electrode of magnesium secondary battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102228128A (en) * 2011-08-12 2011-11-02 重庆大学 Nickel methionine chelate and synthesis method thereof
US20130295469A1 (en) * 2012-05-03 2013-11-07 Ut-Battelle, Llc Lithium sulfide compositions for battery electrolyte and battery electrode coatings
CN103872323A (en) * 2014-03-19 2014-06-18 上海交通大学 Preparation method of nano transition metal sulfide material of positive electrode of magnesium secondary battery

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JINGHUI JIANG等: ""Biomolecule-assisted synthesis of flower-like NiS microcrystals via a hydrothermal process"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108133967A (en) * 2017-11-14 2018-06-08 吉林大学 A kind of ultra-violet (UV) band part reflective semitransparent film and preparation method thereof
CN108133967B (en) * 2017-11-14 2020-01-24 吉林大学 Ultraviolet-region semi-reflecting and semi-permeable membrane and preparation method thereof
CN108597893A (en) * 2018-05-28 2018-09-28 江苏大学 A kind of preparation method based on the composite electrode material for super capacitor in nickel foam

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