CN102071441A - Method for preparing material containing sulfur and nickel - Google Patents
Method for preparing material containing sulfur and nickel Download PDFInfo
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- CN102071441A CN102071441A CN 201010595789 CN201010595789A CN102071441A CN 102071441 A CN102071441 A CN 102071441A CN 201010595789 CN201010595789 CN 201010595789 CN 201010595789 A CN201010595789 A CN 201010595789A CN 102071441 A CN102071441 A CN 102071441A
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Abstract
The invention relates to a method for preparing a material containing sulfur and nickel. The preparation method is as follows: in an electroplating system of nickel-containing electroplate liquid, sulfur-containing compound solution is dropped near a negative plate in the electroplate liquid; the sulfur-containing compound directly reacts with the nickel ions in the electroplate liquid in one step according to the equation below; and on the negative plate, the chemical precipitation of NiS and the electrodeposition of nickel are performed simultaneously to prepare the material containing sulfur and nickel. The reaction product NiS is deposited on the negative electrode; and meanwhile, the electrodeposition of nickel is performed continuously on the negative electrode under the action of the electric field in the electroplating process, namely the chemical precipitation of NiS and the electrodeposition of nickel can be performed simultaneously so as to prepare the material containing sulfur and nickel. The invention has simple process and convenient operation; the new sulfur-containing compound is selected as sulfur source and the codeposition mode combining the chemical precipitation of sulfur with the electrodeposition of nickel is adopted to prepare the material containing sulfur and nickel, thus the sulfur content of the material containing sulfur and nickel is easy to control, and the problem that the material containing sulfur and nickel is difficult to prepare and the sulfur content is difficult to control can be solved; and the product quality is stable, the process flow is short and the large-scale production can be realized.
Description
Technical field
The invention discloses a kind of preparation method of sulfur-bearing nickel material, specifically be meant a kind of method that adopts sedimentary mode behind the nickel sulfonium ion direct reaction to prepare active sulfur-bearing nickel anode material.Belong to technical field of electrochemistry.
Background technology
The sulfur-bearing nickel material mainly is the active anode material as electronickelling industry.Owing to adopt the sulfur-bearing nickel anode can effectively reduce bath voltage, improve sedimentation velocity and electroplating efficiency, the equipment corrosion of avoiding chloride electrolyte system to cause, and obtain advantage such as low-stress coating, become most popular in the world active nickel anode material.
Canada INCO company has monopolized the world market of this product since having developed sulfur-bearing nickel active anode material.To its production technology, particularly to taking strict secrecy provision for sulphur sulphur source.China still is in the stage of fumbling to the production technology of sulfur-bearing nickel at present.The method that current trial in the world prepares sulfur-bearing nickel mainly contains two kinds: the one, adopt to contain=C-SO
2The organism of-group is the electrolytic mode in sulphur source, promptly adds to contain=C-SO in electrolytic solution
2The organics additive of-group progressively is reduced element sulphur and is deposited on the Ni substrate; The 2nd, adopt the mode of vapour deposition, thereby promptly under gaseous phase, make the nickel element sulphur form the sulfur-bearing nickel material by decomposing deposition.Have the quality instability of sulfur-bearing nickel in the production process, sulphur content is difficult to problems such as control.
Summary of the invention
The object of the present invention is to provide that a kind of processing method is simple, easy to operate, technical process is short, be the sulphur source to contain the S compound, by the method for nickel element sulphur direct chemical prepared in reaction sulfur-bearing nickel material in electroplating solution.
The preparation method of a kind of sulfur-bearing nickel material of the present invention is to adopt following proposal to realize:
A kind of preparation method of sulfur-bearing nickel material is in containing the plating system of nickel plating solution, and sulfocompound solution is splashed in the electroplate liquid near the negative plate; On negative plate, the galvanic deposit of NiS electroless plating and nickel is carried out simultaneously, prepares the sulfur-bearing nickel material.
Among the preparation method of a kind of sulfur-bearing nickel material of the present invention, the anode of described plating system adopts metallic nickel or graphite material; Described negative electrode adopts metal titanium or stainless material; Described cathode current density is controlled at 5～10A/dm
2Describedly contain that nickel concentration is 30～100g/L in the nickel plating solution.
Among the preparation method of a kind of sulfur-bearing nickel material of the present invention, the described nickel plating solution that contains is selected from least a in single nickel salt, nickelous chloride, nickel sulfamic acid, the nickel fluoborate solution.
Among the preparation method of a kind of sulfur-bearing nickel material of the present invention, described sulfocompound is selected from least a in hydrogen sulfide, sodium sulphite, potassium sulphide, the ammonium sulfide.
Among the preparation method of a kind of sulfur-bearing nickel material of the present invention, the concentration of described sulfocompound solution is controlled at 0.001～0.01mol/L, and near its rate of addition negative plate is controlled at 0.04～0.2L/dm
2H; The massfraction of the sulphur of the sulfur-bearing nickel material of preparation is 0.02%～0.2%.
The present invention is owing to adopt above-mentioned processing method, and sulfocompound is fed in the electroplate liquid near the negative plate, and under electric field action, the nickel ion in sulfocompound and the electroplate liquid is pressed the direct single step reaction of following formula:
S
2-+Ni
2+→NiS↓
Reaction product NiS is deposited on the negative electrode; Simultaneously, nickel constantly galvanic deposit on negative electrode under electric field action in electroplating process, i.e. the galvanic deposit of the electroless plating of NiS and nickel is carried out simultaneously, thereby prepares the sulfur-bearing nickel material.
By nickel concentration and current density in the control plating bath, with negative electrode and anode water placing flat, the plating of negative electrode is faced up, can on the plating face of negative electrode, obtain the sulfur-bearing nickel material.
The process of the galvanic deposit by the control electroless plating of NiS and nickel is promptly controlled current density, the bath concentration of electroplating process, the addition and the interpolation speed of sulfocompound, can realize effective control of the sulphur content in the sulfur-bearing nickel material.Wherein: current density, bath concentration are according to the nickel content M in the sulfur-bearing nickel material of design
NiCalculate; Because, M
Ni=KQ, K is the electrochemical equivalent of electric deposition nickel, is a constant, promptly 1.095, Q is the ampere-hour number of electroplating process; Therefore, as nickel content M
NiAfter determining, the ampere-hour number of electroplating process can determine, thereby, can determine corresponding current density and electroplating time.After the volume of plating tank is determined, promptly can be according to the nickel content M in the sulfur-bearing nickel material of design
Ni, calculate the initial concentration of electroplate liquid, require the initial concentration of electroplate liquid to separate out M in galvanic deposit
NiAfter, still can keep the works better of the system of electroplating.Conversion obtains the addition of sulfocompound according to the sulphur content in the sulfur-bearing nickel material of design equally; After the addition and electroplating time of determining sulfocompound, then can determine the concentration of sulfocompound solution according to the interpolation speed of being convenient to control.Thereby realize controlling more accurately within the specific limits the sulphur content in the prepared sulfur-bearing nickel material.
In sum; technology of the present invention is simple, easy to operate; by selecting the new S compound sulphur source that contains, adopt the codeposition mode of the galvanic deposit of the electroless plating of sulphur and nickel to prepare the sulfur-bearing nickel material, help controlling the sulphur content of sulfur-bearing nickel material; the difficulty preparation and the unmanageable problem of sulphur content of current sulfur-bearing nickel material have been solved; the sulfur-bearing nickel material of preparing, its sulphur content can be controlled in 0.02%～0.2% scope, constant product quality; technical process is short, can accomplish scale production.
Embodiment
Embodiment 1
Adopt the galvanized mode of solution, adopt the metal nickel plate plate at anode, electroplate liquid adopts single nickel salt and nickel fluoborate to press 1: 2 blended solution of mass ratio, nickel concentration is controlled at 90～100g/L, negative electrode adopts stainless steel plate, the equal horizontal positioned of negative electrode and anode, the plating of negative electrode faces up, and current density is controlled at 9～10A/dm
2Sodium sulphite is selected in the sulphur source, and sodium sulfide solution feeds near the negative electrode with pipeline, and the concentration of sodium sulfide solution is controlled at 0.001～0.002mol/L, and near its rate of addition negative plate is controlled at 0.04～0.06L/dm
2H after the deposition of 100Ah, obtains gross weight and is about 105 grams, and sulphur content is 0.02%～0.04% sulfur-bearing nickel material.
Embodiment 2
Adopt the galvanized mode of solution, anode adopts metal nickel plate, and electroplate liquid adopts nickel sulfamic acid solution, nickel concentration is controlled at 50～60g/L, and negative electrode adopts metallic titanium plate, the equal horizontal positioned of negative electrode and anode, the plating of negative electrode faces up, and current density is controlled at 5～8A/dm
2Sodium sulphite and potassium sulphide are selected in the sulphur source, sodium sulphite and potassium sulphide are pressed 1: 1 blended aqueous solution of mass ratio with near the pipeline feeding negative electrode, the total concn of element sulphur is controlled at 0.004～0.006mol/L in the solution, and near its rate of addition negative plate is controlled at 0.05～0.15L/dm
2H after the deposition of 500Ah, obtains gross weight and is about 540 grams, and sulphur content is 0.08%～0.12% sulfur-bearing nickel material.
Embodiment 3
Adopt the galvanized mode of solution, anode adopts graphite cake, and electroplate liquid adopts nickel chloride solution, nickel concentration is controlled at 30～40g/L, and negative electrode adopts metallic titanium plate, the equal horizontal positioned of negative electrode and anode, the plating of negative electrode faces up, and current density is controlled at 7～10A/dm
2Ammonium sulfide is selected in the sulphur source, and the aqueous solution of ammonium sulfide is fed near the negative electrode with pipeline, and the total concn of element sulphur is controlled at 0.009～0.01mol/L in the solution, and near its rate of addition negative plate is controlled at 0.06～0.1L/dm
2H after the deposition of 800Ah, obtains gross weight and is about 870 grams, and sulphur content is 0.18%～0.2% sulfur-bearing nickel material.
Claims (5)
1. the preparation method of a sulfur-bearing nickel material is characterized in that: in containing the plating system of nickel plating solution, sulfocompound solution is splashed in the electroplate liquid near the negative plate; On negative plate, the galvanic deposit of NiS electroless plating and nickel is carried out simultaneously, prepares the sulfur-bearing nickel material.
2. the preparation method of a kind of sulfur-bearing nickel material according to claim 1 is characterized in that: the anode of described plating system adopts metallic nickel or graphite material; Described negative electrode adopts metal titanium or stainless material; Described cathode current density is controlled at 5～10A/dm
2Describedly contain that nickel concentration is 30～100g/L in the nickel plating solution.
3. the preparation method of a kind of sulfur-bearing nickel material according to claim 2 is characterized in that: the described nickel plating solution that contains is selected from least a in single nickel salt, nickelous chloride, nickel sulfamic acid, the nickel fluoborate solution.
4. the preparation method of a kind of sulfur-bearing nickel material according to claim 3 is characterized in that: described sulfocompound is selected from least a in hydrogen sulfide, sodium sulphite, potassium sulphide, the ammonium sulfide.
5. according to the preparation method of any described a kind of sulfur-bearing nickel material of claim 1～4, it is characterized in that: the concentration of described sulfocompound solution is controlled at 0.001～0.01mol/L, and near its rate of addition negative plate is controlled at 0.04～0.2L/dm
2H; The massfraction of the sulphur of the sulfur-bearing nickel material of preparation is 0.02%～0.2%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010595789 CN102071441A (en) | 2010-12-20 | 2010-12-20 | Method for preparing material containing sulfur and nickel |
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| CN 201010595789 CN102071441A (en) | 2010-12-20 | 2010-12-20 | Method for preparing material containing sulfur and nickel |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106623969A (en) * | 2016-11-23 | 2017-05-10 | 昆明理工大学 | Method of preparing nanometer nickel-sulfur alloy through replacement deposition of low eutectic ionic liquid |
| CN107723769A (en) * | 2017-10-24 | 2018-02-23 | 宝鸡市铭坤有色金属有限公司 | A kind of preparation method of nano-crystal nickel material |
| CN109023440A (en) * | 2018-09-04 | 2018-12-18 | 中国科学院兰州化学物理研究所 | Utilize the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material |
| CN112323096A (en) * | 2020-09-23 | 2021-02-05 | 河北东恩企业管理咨询有限公司 | Preparation method of sulfur-nickel-containing round cake |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0285385A (en) * | 1988-09-22 | 1990-03-26 | Tosoh Corp | Production of electrode |
| JPH02163392A (en) * | 1988-12-15 | 1990-06-22 | Tosoh Corp | 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 |
-
2010
- 2010-12-20 CN CN 201010595789 patent/CN102071441A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0285385A (en) * | 1988-09-22 | 1990-03-26 | Tosoh Corp | Production of electrode |
| JPH02163392A (en) * | 1988-12-15 | 1990-06-22 | Tosoh Corp | 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 |
Non-Patent Citations (1)
| Title |
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| 《天津大学学报》 19911231 覃齐贤等 镍-硫化镍复合物析氢活性阴极的研究 80-84 1-5 , 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106623969A (en) * | 2016-11-23 | 2017-05-10 | 昆明理工大学 | Method of preparing nanometer nickel-sulfur alloy through replacement deposition of low eutectic ionic liquid |
| CN107723769A (en) * | 2017-10-24 | 2018-02-23 | 宝鸡市铭坤有色金属有限公司 | A kind of preparation method of nano-crystal nickel material |
| CN109023440A (en) * | 2018-09-04 | 2018-12-18 | 中国科学院兰州化学物理研究所 | Utilize the carbon-free method taken sulphur agent and prepare sulfur-bearing nickel material |
| CN112323096A (en) * | 2020-09-23 | 2021-02-05 | 河北东恩企业管理咨询有限公司 | Preparation method of sulfur-nickel-containing round cake |
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Application publication date: 20110525 |