CN109023440A - Utilize the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material - Google Patents
Utilize the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material Download PDFInfo
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- CN109023440A CN109023440A CN201811024249.0A CN201811024249A CN109023440A CN 109023440 A CN109023440 A CN 109023440A CN 201811024249 A CN201811024249 A CN 201811024249A CN 109023440 A CN109023440 A CN 109023440A
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- Prior art keywords
- nickel
- carbon
- sulphur agent
- electrolyte
- sulfur
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
Abstract
The carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material is utilized the invention discloses a kind of, utilize the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material, it is to take sulphur agent using the mixed solution of nickel sulfate and nickel chloride as nickel electrolyte with sulfites to be carbon-free, be electrolysed and obtain in constant temperature electrolytic cell.The present invention is added that sulfites are carbon-free to take sulphur agent in nickel electrolyte, sulphite in acidic electrolysis bath with H+SO is released in reaction2, SO in electrolytic process2Reduction reaction occurs to be precipitated in the form of sulphur simple substance in cathode.The present invention controls sulfur content in sulfur-bearing nickel material by adjusting the circulation rate of the molar ratio of sulfate radical and chloride ion in nickel electrolyte, the temperature of electrolytic process, time, current density and electrolyte.It is 0.0015 ~ 0.0055% using the sulfur-bearing nickel material sulfur content that this method obtains, carbon content is 0.0009 ~ 0.0012%, has sulfur content controllable, the lower feature of carbon content in material.
Description
Technical field
The present invention relates to a kind of preparation method of sulfur-bearing nickel material more particularly to a kind of take sulphur agent using carbon-free and prepare sulfur-bearing
The method of nickel material, belongs to electrochemical technology field.
Background technique
Sulfur-bearing nickel material is a kind of plating active anode material.Current efficiency can be improved using sulfur-bearing nickel anode, have
Effect reduces tank voltage, to improve cathode deposition rate.The method for producing sulfur-bearing nickel material includes vapour deposition process and electrolysis method.
Vapour deposition process decomposes deposition after mixing carbonyl nickel steam, CO gas, sulfurous gas or sulfur-bearing crystal seed and forms sulfur-bearing nickel material
There is the disadvantages of this production process complicated, energy consumption height, unstable product quality in material, the method.Sulfur-bearing nickel is prepared using electrolysis method, is
Sulphur agent will be taken to be added into nickel electrolyte, deposit to obtain sulfur-bearing nickel in cathode.Be often used at present take sulphur agent be thiocarbamide etc. containing=
C-SO2The organic matter of group adds and this organic take sulphur agent to will lead to carbon content in product higher.To solve this problem, it needs
It finds a kind of using the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material.
Summary of the invention
The carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material is utilized the purpose of the present invention is to provide a kind of.
The present invention is the mixed solution with nickel sulfate and nickel chloride using the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material
For nickel electrolyte, sulphur agent is taken to be carbon-free with sulfites, is prepared using electrolysis method.Its specifically comprises the processes of: is by sulfurous acid
Saline solution is added in nickel electrolyte, and being sufficiently stirred, which makes to take sulphur agent, is uniformly dispersed；It will add again containing the nickel electrolyte for taking sulphur agent
Enter in the electrolytic cell with heating device, to 40 ~ 80 DEG C, constant temperature is electrolysed 5 ~ 6 hours heating nickel electrolyte.
In nickel electrolyte, the molar ratio of sulfate radical and chloride ion is 1:1.6, and nickel ion concentration is 60 ~ 80g/L.
The carbon-free sulphur agent sulfites of taking are sodium sulfite, ammonium sulfite, sodium pyrosulfite；It is described containing taking sulphur agent
Nickel electrolyte in, take the concentration of sulphur agent in terms of S, be 0.05 ~ 0.5g/L.
The anode plate of the electrolytic cell is pure nickel plate, and cathode plate is Titanium board.The current density of the electrolytic process be 80 ~
220A/m2。
To maintain sulfur content in electrolyte to stablize, in electrolytic process, containing taking the nickel electrolyte of sulphur agent constantly from head tank stream
Enter electrolytic cell, while the electrolyte in electrolytic cell is flowed out with identical speed from lower liquid mouth, electrolyte circulation rate be 0.62 ~
1.85L/dm2·h。
The present invention is added that sulfites are carbon-free to take sulphur agent in nickel electrolyte, sulphite in acidic electrolysis bath with H+Reaction
Release SO2, SO in electrolytic process2Reduction reaction occurs to be precipitated in the form of sulphur simple substance in cathode.Its reaction principle is as follows:
SO3 2- + H+ = HSO3 -
HSO3- +H+=SO2 + H2O
Cell reaction equation:
Cathode: SO2+ 4H+ + 4e →S + H2O
Anode: H2O - 4e → O2 + 4H+
Overall reaction: SO2 → S + O2
The present invention has the advantage that compared with the prior art
1, take sulphur agent using carbon-free, do not introduce carbon impurity in electrolytic process, make in sulfur-bearing nickel material product that carbon content is lower: carbon contains
Amount is 0.0009 ~ 0.0012%；
2, it uses the mixed solution of nickel sulfate and nickel chloride for nickel electrolyte, and adjusts the molar ratio of sulfate radical and chloride ion, electricity
The temperature of solution preocess, the time, current density and electrolyte circulation rate control sulfur-bearing nickel material in sulfur content be 0.0015
~0.0055%。
Specific embodiment
It is described further below by the method that specific embodiment prepares sulfur-bearing nickel material to the present invention.
Embodiment 1
(1) sodium sulfite for taking certain mass obtains sodium sulfite solution with a small amount of deionized water dissolving；Sodium sulfite is molten
Liquid is added in the nickel electrolyte of the mixed solution composition of nickel sulfate and nickel chloride, stirs 5 minutes, sodium sulfite is made to be uniformly dispersed.
The concentration of nickel electrolyte sulfite sodium is 0.05g/L in terms of S；In the mixing point solution liquid of nickel sulfate and nickel chloride, sulfate radical with
The molar ratio of chloride ion is 1:1.6, nickel ion concentration 60g/L.
(2) nickel electrolyte containing sodium sulfite is added in the electrolytic cell with heating device, heating electrolyte to 40
Remain temperature-resistant after DEG C, in current density 80A/m2Lower electrolysis 6 hours.To maintain sulfur content in electrolyte to stablize, it is being electrolysed
Constantly flow into electrolytic cell from head tank containing taking the electrolyte of sulphur agent in the process, at the same the electrolyte in electrolytic cell with identical speed from
Lower liquid mouth outflow, electrolyte circulation rate are 0.62L/dm2·h。
Through detecting, sulfur content is 0.0014% in cathode nickel sheet, phosphorus content 0.001%.
Embodiment 2
(1) sodium sulfite for taking certain mass obtains sodium sulfite solution with a small amount of deionized water dissolving；Sodium sulfite is molten
Liquid is added in the nickel electrolyte of the mixed solution composition of nickel sulfate and nickel chloride, stirs 5 minutes, sodium sulfite is made to be uniformly dispersed.
The concentration of nickel electrolyte sulfite sodium is 0.1g/L in terms of S；In the mixed electrolytic solution of nickel sulfate and nickel chloride, sulfate radical with
The molar ratio of chloride ion is 1:1.6, nickel ion concentration 70g/L.
(2) nickel electrolyte containing sodium sulfite is added in the electrolytic cell with heating device, heating electrolyte to 65
Remain temperature-resistant after DEG C, in current density 110A/m2Lower electrolysis 6 hours.To maintain sulfur content in electrolyte to stablize, it is being electrolysed
The electrolyte containing sodium sulfite constantly flows into electrolytic cell from head tank in the process, while the electrolyte in electrolytic cell is with identical speed
It is flowed out from lower liquid mouth, electrolyte circulation rate is 1.23L/dm2·h。
Through detecting, sulfur content is 0.0047% in cathode nickel sheet, carbon content 0.0009%.
Embodiment 3
(1) ammonium sulfite for taking certain mass obtains ammonium sulfite solution with a small amount of deionized water dissolving；Ammonium sulfite is molten
Liquid is added in the nickel electrolyte of the mixed solution composition of nickel sulfate and nickel chloride, stirs 5 minutes, ammonium sulfite is made to be uniformly dispersed.
The concentration of nickel electrolyte sulfite ammonium is 0.15g/L in terms of S；In the mixed electrolytic solution of nickel sulfate and nickel chloride, sulfate radical with
The molar ratio of chloride ion is 1:1.6, nickel ion concentration 80g/L.
(2) nickel electrolyte containing ammonium sulfite is added in the electrolytic cell with heating device, heating electrolyte to 70
Remain temperature-resistant after DEG C, in current density 110A/m2Lower electrolysis 6 hours.To maintain sulfur content in electrolyte to stablize, it is being electrolysed
The electrolyte containing ammonium sulfite constantly flows into electrolytic cell from head tank in the process, while the electrolyte in electrolytic cell is with identical speed
It is flowed out from lower liquid mouth, electrolyte circulation rate is 1.85L/dm2·h。
Through detecting, sulfur content is 0.0055% in cathode nickel sheet, carbon content 0.0012%.
Embodiment 4
(1) sodium pyrosulfite for taking certain mass obtains sodium metabisulfite solution with a small amount of deionized water dissolving；By burnt sulfurous
Acid sodium solution is added in the nickel electrolyte of the mixed solution composition of nickel sulfate and nickel chloride, stirs 5 minutes, makes sodium pyrosulfite point
It dissipates uniform.The concentration of sodium pyrosulfite is 0.5g/L in terms of S in nickel electrolyte；In the mixing point solution liquid of nickel sulfate and nickel chloride,
The molar ratio of sulfate radical and chloride ion is 1:1.6, nickel ion concentration 80g/L.
(2) nickel electrolyte containing sodium pyrosulfite is added in the electrolytic cell with heating device, heating electrolyte is extremely
Remain temperature-resistant after 80 DEG C, in current density 220A/m2Lower electrolysis 6 hours.To maintain sulfur content in electrolyte to stablize, in electricity
Electrolyte in solution preocess containing sodium pyrosulfite constantly flows into electrolytic cell from head tank, while the electrolyte in electrolytic cell is with identical
Speed is flowed out from lower liquid mouth, and electrolyte circulation rate is 1.85L/dm2·h。
Through detecting, sulfur content is 0.0050% in cathode nickel sheet, carbon content 0.0009%.
In the various embodiments described above, the anode plate of electrolytic cell is pure nickel plate, and cathode plate is Titanium board.
Claims (8)
1. being using the mixed solution of nickel sulfate and nickel chloride as nickel electrowinning using the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material
Liquid is taken sulphur agent with sulfites to be carbon-free, is prepared using electrolysis method.
2. utilizing the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material as described in claim 1, it is characterised in that: by sulphite
Class solution is added in nickel electrolyte, and being sufficiently stirred, which makes to take sulphur agent, is uniformly dispersed；It will be added again containing the nickel electrolyte for taking sulphur agent
In electrolytic cell with heating device, to 40 ~ 80 DEG C, constant temperature is electrolysed 5 ~ 6 hours heating nickel electrolyte.
3. utilizing the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material as claimed in claim 1 or 2, it is characterised in that: its feature
Be: the carbon-free sulphur agent sulfites of taking are sodium sulfite, ammonium sulfite, sodium pyrosulfite.
4. utilizing the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material as claimed in claim 1 or 2, it is characterised in that: its feature
Be: in nickel electrolyte, the molar ratio of sulfate radical and chloride ion is 1:1.6, and nickel ion concentration is 60 ~ 80g/L.
5. utilizing the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material as claimed in claim 2, it is characterised in that: described containing taking
In the nickel electrolyte of sulphur agent, the concentration of sulphur agent is taken in terms of S, is 0.05 ~ 0.5g/L.
6. utilizing the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material as claimed in claim 2, it is characterised in that: its feature exists
In: the current density of the electrolytic process is 80 ~ 220A/m2。
7. utilizing the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material as claimed in claim 2, it is characterised in that: electrolytic process
In, constantly flow into electrolytic cell from head tank containing the nickel electrolyte of sulphur agent is taken, while the electrolyte in electrolytic cell with identical speed from
Lower liquid mouth outflow, electrolyte circulation rate are 0.62 ~ 1.85L/dm2·h。
8. utilizing the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material as claimed in claim 2, it is characterised in that: the electrolytic cell
Anode plate be pure nickel plate, cathode plate is Titanium board.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811024249.0A CN109023440A (en) | 2018-09-04 | 2018-09-04 | Utilize the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811024249.0A CN109023440A (en) | 2018-09-04 | 2018-09-04 | Utilize the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material |
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| CN109023440A true CN109023440A (en) | 2018-12-18 |
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| CN201811024249.0A Pending CN109023440A (en) | 2018-09-04 | 2018-09-04 | Utilize the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112593273A (en) * | 2020-12-07 | 2021-04-02 | 中国科学院宁波材料技术与工程研究所 | Metal/sulfur-nickel-containing composite material and preparation method and application thereof |
| CN112680633A (en) * | 2020-12-07 | 2021-04-20 | 迈瑞沙(宁波)新材料科技有限公司 | Nickel-cobalt-sulfur composite material and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2392708A (en) * | 1941-06-13 | 1946-01-08 | Int Nickel Co | Method of making sulphur-containing nickel anodes electrolytically |
| CA842212A (en) * | 1970-05-19 | C. Castell Henry | Anode for the electrodeposition of nickel | |
| US4087339A (en) * | 1976-07-02 | 1978-05-02 | The International Nickel Company, Inc. | Electrowinning of sulfur-containing nickel |
| US4330380A (en) * | 1979-11-21 | 1982-05-18 | Falconbridge Nickel Mines Limited | Electrodeposition of sulfur-bearing nickel |
| JPS58147577A (en) * | 1982-02-24 | 1983-09-02 | Toyo Soda Mfg Co Ltd | Production of electrode |
| CN1844462A (en) * | 2006-03-16 | 2006-10-11 | 郑州大学 | Ni-S active cathode for hydrogen evolution with gradient structure and method for preparing same |
| CN102071441A (en) * | 2010-12-20 | 2011-05-25 | 中南大学 | Method for preparing material containing sulfur and nickel |
| CN103160868A (en) * | 2011-12-17 | 2013-06-19 | 鞍钢重型机械有限责任公司 | Electrolyte for producing active nickel with sulfur and use method thereof |
| CN104213150A (en) * | 2014-07-04 | 2014-12-17 | 襄阳化通化工有限责任公司 | Sulfur-containing active nickel briquette produced through electrolytic process |
-
2018
- 2018-09-04 CN CN201811024249.0A patent/CN109023440A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA842212A (en) * | 1970-05-19 | C. Castell Henry | Anode for the electrodeposition of nickel | |
| US2392708A (en) * | 1941-06-13 | 1946-01-08 | Int Nickel Co | Method of making sulphur-containing nickel anodes electrolytically |
| US4087339A (en) * | 1976-07-02 | 1978-05-02 | The International Nickel Company, Inc. | Electrowinning of sulfur-containing nickel |
| US4330380A (en) * | 1979-11-21 | 1982-05-18 | Falconbridge Nickel Mines Limited | Electrodeposition of sulfur-bearing nickel |
| JPS58147577A (en) * | 1982-02-24 | 1983-09-02 | Toyo Soda Mfg Co Ltd | Production of electrode |
| CN1844462A (en) * | 2006-03-16 | 2006-10-11 | 郑州大学 | Ni-S active cathode for hydrogen evolution with gradient structure and method for preparing same |
| CN102071441A (en) * | 2010-12-20 | 2011-05-25 | 中南大学 | Method for preparing material containing sulfur and nickel |
| CN103160868A (en) * | 2011-12-17 | 2013-06-19 | 鞍钢重型机械有限责任公司 | Electrolyte for producing active nickel with sulfur and use method thereof |
| CN104213150A (en) * | 2014-07-04 | 2014-12-17 | 襄阳化通化工有限责任公司 | Sulfur-containing active nickel briquette produced through electrolytic process |
Non-Patent Citations (1)
| Title |
|---|
| 陈治良: "《电镀车间技术指南》", 31 May 2007, 国防工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112593273A (en) * | 2020-12-07 | 2021-04-02 | 中国科学院宁波材料技术与工程研究所 | Metal/sulfur-nickel-containing composite material and preparation method and application thereof |
| CN112680633A (en) * | 2020-12-07 | 2021-04-20 | 迈瑞沙(宁波)新材料科技有限公司 | Nickel-cobalt-sulfur composite material and preparation method and application thereof |
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Application publication date: 20181218 |