CN102839402A - Iron tin stibium phosphorus alloy with high phosphorus content and preparation method thereof - Google Patents
Iron tin stibium phosphorus alloy with high phosphorus content and preparation method thereof Download PDFInfo
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- CN102839402A CN102839402A CN2012103662739A CN201210366273A CN102839402A CN 102839402 A CN102839402 A CN 102839402A CN 2012103662739 A CN2012103662739 A CN 2012103662739A CN 201210366273 A CN201210366273 A CN 201210366273A CN 102839402 A CN102839402 A CN 102839402A
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Abstract
The invention provides an iron tin stibium phosphorus alloy with high phosphorus content and a preparation method thereof and relates to an electroplated alloy. The raw material of the alloy comprises the following components: 35-45 parts of boric acid, 55-65 parts of ammonia chloride, 15-25 parts of ammonium bromide, 30-45 parts of sodium hypophosphite, 5-15 parts of ferrous chloride, 2-8 parts of stannous chloride, 4-10 parts of antimony potassium tartrate and 1-3 parts of ascorbic acid. The preparation method for an electroplated iron tin stibium phosphorus alloy solution with high phosphorus content comprises the following steps: 1) dissolving boric acid in hot water of which the volume is 1/2 of the total volume, and adding ammonia chloride, ammonium bromide, sodium hypophosphite and ascorbic acid under a stirring condition, thereby obtaining a solution A after dissolving, wherein the dosage of water is 40%-60% of the total weight of the electroplated iron tin stibium phosphorus alloy solution with high phosphorus content, and 2) adjusting the pH of the solution A as 2, and then adding ferrous chloride, stannous chloride, antimony potassium tartrate and ascorbic acid, adding water to a specified volume, and electrolyzing, thereby obtaining the electroplated iron tin stibium phosphorus alloy solution with high phosphorus content.
Description
Technical field
The present invention relates to a kind of plating alloy, relate in particular to a kind of plating high content of phosphorus iron tin antimony phosphorus alloy and preparation method thereof.
Background technology
Advantages such as that plating has is with low cost, technology is simple, easy to operate, it is used very extensively, and is closely bound up with all respects of life, and plating is one of effective means in the process for treating surface.Past mainly is to electroplate monometallic, far can not satisfy the demand of modernization to surface property at present.Therefore, plating alloy is in nearly more than 20 years developing rapidly, and it not only can obtain the surface of property, and of a great variety, and range of application is more extensive, has been applied to the lithium cell industry at present.Plating alloy is meant the process that adopts electrochemical method to make two or more metal codeposition.At present, the alloy of studying has both at home and abroad surpassed kind more than 250 but the plating alloy of practical application kind more than 40 only.
Summary of the invention
The object of the present invention is to provide a kind of good stability, solidity to corrosion strong, cheap, be mainly used in the surface finishing of miscellaneous hardware etc. and the high content of phosphorus iron tin antimony phosphorus alloy of lithium ion battery negative material.
Another object of the present invention is to provide a kind of preparation method who electroplates high content of phosphorus iron tin antimony phosphorus alloy solution.
The raw material of said high content of phosphorus iron tin antimony phosphorus alloy is formed: boric acid 35～45, ammonia chloride 55～65, ammonia bromide 15～25, inferior sodium phosphate 30～45, iron protochloride 5～15, tin protochloride 2～8, antimonypotassium tartrate 4～10 and xitix 1～3.
The raw material composition of said high content of phosphorus iron tin antimony phosphorus alloy can be preferably by mass ratio: boric acid 38～42, ammonia chloride 58～62, ammonia bromide 18～25, inferior sodium phosphate 38～42, iron protochloride 8～13, tin protochloride 4～7, antimonypotassium tartrate 5～8 and xitix 1.5～2.5.
The raw material of said high content of phosphorus iron tin antimony phosphorus alloy is formed and is preferably by mass ratio: 2 parts in 40 parts of boric acid, 60 parts of ammonia chlorides, 20 parts of ammonia bromides, 40 parts of inferior sodium phosphate, 10 parts of iron protochlorides, 4 parts of tin protochlorides, 8 parts of antimonypotassium tartrates and xitix.
The preparation method of said plating high content of phosphorus iron tin antimony phosphorus alloy solution may further comprise the steps:
1) boric acid is dissolved in the warm water of TV 1/2, stirs adding ammonium chloride, brometo de amonio, inferior sodium phosphate and xitix down, obtain solution A after the dissolving; The consumption of said water can be electroplates 40% ~ 60% of high content of phosphorus iron tin antimony phosphorus alloy solution total mass;
2) pH of adjustment solution A is 2, adds iron protochloride, tin protochloride, antimonypotassium tartrate and xitix then, adds water to prescribed volume, promptly gets after the electrolysis and electroplates high content of phosphorus iron tin antimony phosphorus alloy solution.
The present invention and existing alloy plating compared with techniques have advantage: the atom content phosphorus of each component accounts for 18%～28% in this alloy, and iron accounts for 40%～48%, tin be 16%～22% with antimony be 8%～14%.Because the content of phosphorus is high, thereby demonstrates strong solidity to corrosion, the alloy good stability is cheap simultaneously, long service life.Simultaneously, phosphorus and tin have very high lithium storage content.Be mainly used in the surface finishing and the lithium ion battery negative material of miscellaneous hardware etc. by the high content of phosphorus iron tin antimony phosphorus alloy of the present invention preparation.
Description of drawings
Fig. 1 is X-ray powder diffraction (XRD) figure of embodiment 1 gained high content of phosphorus iron tin antimony phosphorus alloy powder negative material.In Fig. 1, X-coordinate is diffraction angle 2-Theta/ °, and ordinate zou is intensity I ntensity/a.u, being labeled as of each diffraction peak: ■ SnSb; ▲ FeSb
2★ Fe
83P
17
Fig. 2 is embodiment 1 gained high content of phosphorus iron tin antimony phosphorus alloy negative material electronic spectrum (EDS) figure.In Fig. 2, X-coordinate is energy E nergy/keV., and ordinate zou is power spectrum intensity I ntensitv/a.u.; In Fig. 2, show Fe, P, Sb, Sn, Cu and O spectrum peak.
Fig. 3 be embodiment 1 gained high content of phosphorus iron tin antimony phosphorus alloy electrode charge and discharge cycles and efficiency curve.Charging and discharging currents density is 100mA/g; X-coordinate is cycle number (Cycle number); Left side ordinate zou is charging capacity Capacity/mAhg
-1Right ordinate zou is coulombic efficiency (Coulomb efficiency)/%, and each mark is represented respectively: the ■ discharge; ● charging; ▲ efficient.
Embodiment
A kind of plating high content of phosphorus iron tin antimony phosphorus alloy, the ratio of weight and number of contained each composition are 2 parts in 40 parts of boric acid, 60 parts of ammonia chlorides, 20 parts of ammonia bromides, 40 parts of inferior sodium phosphate, 10 parts of iron protochlorides, 4 parts of tin protochlorides, 8 parts of antimonypotassium tartrates and xitix.With the plane copper is that negative electrode carries out plating 20min, obtains iron tin antimony phosphorus alloy material.XRD result among Fig. 1 shows that the thing of material is SnSb mutually, FeSb
2, Fe
83P
17The Kuan Huafeng that about 45 °, occurs shows that it has non-crystalline state thing phase.It is consistent with the XRD of non-crystalline state Fe-P alloy.EDS result (Fig. 2) shows that Cu is the substrate peak, and O is an impurity peaks, and after the normalization method, the atom content phosphorus of each component accounts for 24% in this alloy, and iron accounts for 45%, tin be 19% with antimony be 10%.With this alloy electrode is test electrode; With the metal lithium sheet is counter electrode; (1: 1: 1v/v), barrier film was Celgard 2400 to electrolytic solution 1M LiPF6/EC (NSC 11801): DMC (methylcarbonate): DEC (diethyl carbonate), in being full of the glove box of argon gas, was assembled into 2025 type button cells; Then on the Land battery test system, with 100mAg
-1Charge-discharge magnification carry out charge-discharge test.Its charge-discharge performance and coulombic efficiency are as shown in Figure 3.Embedding lithium capacity is 1171 mAh g first
-1, taking off the lithium capacity is 783mAh/g, coulombic efficiency is 67% first.After 80 all charge and discharge cycles, its capacity still remains on 627mAh g
-1, far above present business-like carbon negative electrode material of lithium ion cell capacity (372mAh g
-1).Since the 3rd week, its coulombic efficiency perseverance remains on more than 96%.Therefore, it is that a kind of comparatively ideal lithium ion battery substitutes negative material, and the preparation method is simple, can accomplish scale production.
Above-mentioned a kind of compound method of electroplating high content of phosphorus iron tin antimony phosphorus alloy solution:
1) boric acid is dissolved in the warm water of TV 1/2 by formulation ratio, stirs adding ammonium chloride, brometo de amonio, inferior sodium phosphate and xitix down, obtain solution A after the dissolving;
2) pH of adjustment solution A is 2, slowly adds iron protochloride, tin protochloride, antimonypotassium tartrate and xitix then, adds water to prescribed volume, can try plating behind the electrolysis 2h.
Embodiment 2
A kind of plating high content of phosphorus iron tin antimony phosphorus alloy, the ratio of weight and number of contained each composition are 3 parts in 35 parts of boric acid, 65 parts of ammonia chlorides, 25 parts of ammonia bromides, 45 parts of inferior sodium phosphate, 15 parts of iron protochlorides, 8 parts of tin protochlorides, 10 parts of antimonypotassium tartrates and xitix.Other is with embodiment 1.EDS result shows that the atom content phosphorus of each component in this alloy accounts for 18%, and iron accounts for 48%, tin be 22% with antimony be 12%.
Embodiment 3
A kind of plating high content of phosphorus iron tin antimony phosphorus alloy, the ratio of weight and number of contained each composition are 1 part in 45 parts of boric acid, 55 parts of ammonia chlorides, 15 parts of ammonia bromides, 30 parts of inferior sodium phosphate, 5 parts of iron protochlorides, 2 parts of tin protochlorides, 4 parts of antimonypotassium tartrates and xitix.Other is with embodiment 1.The atom content phosphorus of each component accounts for 25% in this alloy, and iron accounts for 45%, tin be 16% with antimony be 14%.
Embodiment 4
A kind of plating high content of phosphorus iron tin antimony phosphorus alloy, the ratio of weight and number of contained each composition are 2.5 parts in 38 parts of boric acid, 62 parts of ammonia chlorides, 42 parts of ammonia bromides, 25 parts of inferior sodium phosphate, 13 parts of iron protochlorides, 7 parts of tin protochlorides, 8 parts of antimonypotassium tartrates and xitix.Other is with embodiment 1.The atom content phosphorus of each component accounts for 23% in this alloy, and iron accounts for 48%, tin be 21% with antimony be 8%.
Embodiment 5
A kind of plating high content of phosphorus iron tin antimony phosphorus alloy, the ratio of weight and number of contained each composition are 1.5 parts in 42 parts of boric acid, 58 parts of ammonia chlorides, 38 parts of ammonia bromides, 18 parts of inferior sodium phosphate, 8 parts of iron protochlorides, 4 parts of tin protochlorides, 5 parts of antimonypotassium tartrates and xitix.Other is with embodiment 1.The atom content phosphorus of each component accounts for 28% in this alloy, and iron accounts for 40%, tin be 20% with antimony be 12%.
Claims (4)
1. high content of phosphorus iron tin antimony phosphorus alloy is characterized in that it is boric acid 35～45, ammonia chloride 55～65, ammonia bromide 15～25, inferior sodium phosphate 30～45, iron protochloride 5～15, tin protochloride 2～8, antimonypotassium tartrate 4～10 and xitix 1～3 that its raw material is formed by mass ratio.
2. high content of phosphorus iron tin antimony phosphorus alloy as claimed in claim 1 is characterized in that it is boric acid 38～42, ammonia chloride 58～62, ammonia bromide 18～25, inferior sodium phosphate 38～42, iron protochloride 8～13, tin protochloride 4～7, antimonypotassium tartrate 5～8 and xitix 1.5～2.5 that its raw material is formed by mass ratio.
3. high content of phosphorus iron tin antimony phosphorus alloy as claimed in claim 2 is characterized in that it is 2 parts in 40 parts of boric acid, 60 parts of ammonia chlorides, 20 parts of ammonia bromides, 40 parts of inferior sodium phosphate, 10 parts of iron protochlorides, 4 parts of tin protochlorides, 8 parts of antimonypotassium tartrates and xitix that its raw material is formed by mass ratio.
4. electroplate the preparation method of high content of phosphorus iron tin antimony phosphorus alloy solution, it is characterized in that may further comprise the steps:
1) boric acid is dissolved in the warm water of TV 1/2, stirs adding ammonium chloride, brometo de amonio, inferior sodium phosphate and xitix down, obtain solution A after the dissolving; The consumption of said water can be electroplates 40% ~ 60% of high content of phosphorus iron tin antimony phosphorus alloy solution total mass;
2) pH of adjustment solution A is 2, adds iron protochloride, tin protochloride, antimonypotassium tartrate and xitix then, adds water to prescribed volume, promptly gets after the electrolysis and electroplates high content of phosphorus iron tin antimony phosphorus alloy solution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104790000A (en) * | 2014-12-10 | 2015-07-22 | 中国计量学院 | Manganese-bismuth-iron-phosphor permanent magnetic alloy plating solution and preparation method thereof |
| CN109440149A (en) * | 2018-11-23 | 2019-03-08 | 云南师范大学 | A kind of plating high-speed rail-low tin content electroplate liquid composition and technique |
| CN109778259A (en) * | 2019-01-04 | 2019-05-21 | 中国计量大学 | A kind of antimony electroplating solution and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051060A (en) * | 1990-11-10 | 1991-05-01 | 机械电子工业部武汉材料保护研究所 | Electric depositing solution of antiwear non-crystal alloy of iron, nickel, phosphorus and technology thereof |
| CN1978710A (en) * | 2005-12-09 | 2007-06-13 | 中国科学院兰州化学物理研究所 | Electro-deposition method of nickel-phosphorus alloy coating |
-
2012
- 2012-09-27 CN CN2012103662739A patent/CN102839402A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051060A (en) * | 1990-11-10 | 1991-05-01 | 机械电子工业部武汉材料保护研究所 | Electric depositing solution of antiwear non-crystal alloy of iron, nickel, phosphorus and technology thereof |
| CN1978710A (en) * | 2005-12-09 | 2007-06-13 | 中国科学院兰州化学物理研究所 | Electro-deposition method of nickel-phosphorus alloy coating |
Non-Patent Citations (1)
| Title |
|---|
| XIAO-MEI ZHENG ET AL.: "A dicranopteris-like Fe–Sn–Sb–P alloy as a promising anode for lithium ion batteries（Supporting Information）", 《CHEM.COMMUN.》, vol. 48, 9 May 2012 (2012-05-09) * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104790000A (en) * | 2014-12-10 | 2015-07-22 | 中国计量学院 | Manganese-bismuth-iron-phosphor permanent magnetic alloy plating solution and preparation method thereof |
| CN104790000B (en) * | 2014-12-10 | 2018-10-26 | 中国计量学院 | A kind of manganese bismuth iron phosphorus permanent-magnet alloy electroplate liquid and preparation method thereof |
| CN109440149A (en) * | 2018-11-23 | 2019-03-08 | 云南师范大学 | A kind of plating high-speed rail-low tin content electroplate liquid composition and technique |
| CN109778259A (en) * | 2019-01-04 | 2019-05-21 | 中国计量大学 | A kind of antimony electroplating solution and preparation method thereof |
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Application publication date: 20121226 |