CN102659173A - Preparation method of battery-grade zinc bromide - Google Patents
Preparation method of battery-grade zinc bromide Download PDFInfo
- Publication number
- CN102659173A CN102659173A CN2012101500246A CN201210150024A CN102659173A CN 102659173 A CN102659173 A CN 102659173A CN 2012101500246 A CN2012101500246 A CN 2012101500246A CN 201210150024 A CN201210150024 A CN 201210150024A CN 102659173 A CN102659173 A CN 102659173A
- Authority
- CN
- China
- Prior art keywords
- zinc bromide
- zinc
- hours
- battery
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 title claims abstract description 46
- 229940102001 zinc bromide Drugs 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012141 concentrate Substances 0.000 claims abstract description 8
- 239000002657 fibrous material Substances 0.000 claims abstract description 7
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 5
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 5
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 5
- 239000011425 bamboo Substances 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 240000006240 Linum usitatissimum Species 0.000 claims 1
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 238000010790 dilution Methods 0.000 claims 1
- 239000012895 dilution Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 14
- 239000000706 filtrate Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000012776 electronic material Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 150000003751 zinc Chemical class 0.000 abstract 1
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 241001330002 Bambuseae Species 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 241000208202 Linaceae Species 0.000 description 3
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Hybrid Cells (AREA)
Abstract
本发明属于电子材料领域，涉及一种电池级溴化锌的制备方法。本发明提出的制备方法是将锌粉置于去离子水中，滴加溴单质，搅拌24小时，过滤；将滤液稀释，与天然纤维材料混和，搅拌24小时，过滤，浓缩，得电池级溴化锌。本发明制备的溴化锌具有以下优点：（1）纯度高，大于99.99%；（2）工艺简单，适合于大规模生产；（3）原材料易得，生产成本低。本发明制备的溴化锌可广泛于高容量可充电池、高效率太阳能电池等工业领域。The invention belongs to the field of electronic materials and relates to a preparation method of battery-grade zinc bromide. The preparation method proposed by the present invention is to place zinc powder in deionized water, add bromine element dropwise, stir for 24 hours, and filter; dilute the filtrate, mix it with natural fiber materials, stir for 24 hours, filter, and concentrate to obtain battery-grade brominated zinc. The zinc bromide prepared by the invention has the following advantages: (1) high purity, greater than 99.99%; (2) simple process, suitable for large-scale production; (3) easy to obtain raw materials, low production cost. The zinc bromide prepared by the invention can be widely used in high-capacity rechargeable batteries, high-efficiency solar batteries and other industrial fields.
Description
技术领域 technical field
本发明属于电子材料技术领域，具体涉及一种电池级溴化锌的制备方法。 The invention belongs to the technical field of electronic materials, and in particular relates to a preparation method of battery-grade zinc bromide.
背景技术 Background technique
溴化锌主要用作海洋石油钻井完井液，固井液，修井液，也是医药工业的一种重要原料。高技术应用领域如可充电池、光电子器件等电子材料对溴化锌质量的要求很高，工业级溴化锌必须通过精制除去其中的无机盐类等杂质才能达到各种不同专用品的质量指标要求。 Zinc bromide is mainly used as offshore oil drilling and completion fluid, cementing fluid, workover fluid, and is also an important raw material in the pharmaceutical industry. High-tech applications such as rechargeable batteries, optoelectronic devices and other electronic materials have high requirements on the quality of zinc bromide. Industrial-grade zinc bromide must be refined to remove impurities such as inorganic salts in order to achieve the quality indicators of various special products. Require.
锌溴液流电池的电解液为溴化锌水溶液，充电过程中，锌以金属形态沉积在导电塑料电极表面，溴形成油状配合物，贮存于正极电解液的底部，其较高的能量密度和功率密度以及优越的循环充放电性能(100％深度放电几千次)使锌溴液流电池具有极高的研究和应用价值。 The electrolyte of the zinc-bromine flow battery is zinc bromide aqueous solution. During the charging process, zinc is deposited on the surface of the conductive plastic electrode in the form of metal, and bromine forms an oily complex, which is stored at the bottom of the positive electrolyte. Its high energy density and Power density and superior cycle charge and discharge performance (thousands of 100% deep discharges) make zinc-bromine flow batteries have extremely high research and application value.
染料敏化太阳能电池（DSSC），也称为“Gratzel cell” 。目前最成功的是Gratzel等人提出的染料敏化纳米二氧化钛薄膜为光阳极的太阳能光电池(简称为Gratzel电池)，其光电转换效率在模拟日光照射下(AM1.5，1000W·m-2 )已达10%。溴化锌常作为染料敏化太阳能电池的电解液介质。 Dye-sensitized solar cell (DSSC), also known as "Gratzel cell". At present, the most successful one is the dye-sensitized nano-titanium dioxide film proposed by Gratzel et al . The solar photovoltaic cell (referred to as the Gratzel cell) as the photoanode. up to 10%. Zinc bromide is often used as the electrolyte medium for dye-sensitized solar cells.
溴化锌的制备方法主要有：（1）锌粉与氢溴酸反应。由于反应过程产生大量氢气，在工业生产中较少使用。（2）锌粉与溴单质反应。通常反应是在高温条件下（～500℃）进行，同时需要在氮气与溴化氢的氛围中，反应条件比较苛刻。常规条件下制备的溴化锌纯度不高，为98％左右。将其提纯为电池级产品的主要方法是真空升华，不但需要消耗大量的能源，而且无法实现大规模生产。 The preparation methods of zinc bromide mainly include: (1) Reaction of zinc powder with hydrobromic acid. Due to the large amount of hydrogen produced in the reaction process, it is rarely used in industrial production. (2) Zinc powder reacts with bromine. Usually the reaction is carried out under high temperature conditions (~500°C), and at the same time, it needs to be in the atmosphere of nitrogen and hydrogen bromide, and the reaction conditions are relatively harsh. The purity of zinc bromide prepared under conventional conditions is not high, about 98%. The main method of purifying it into battery-grade products is vacuum sublimation, which consumes a lot of energy and cannot be mass-produced.
天然纤维素材料，如棉花、竹纤维、亚麻等表面含有多种活性基团，如羧基、羰基、羟基等，能够从溶液中选择性吸收铅、铬、镉、铁、铜、钴等重金属元素，从而实现溴化锌的纯化。与升华工艺相比，天然纤维素材料吸附提纯工艺几乎不消耗能源，可以实现大规模生产；不仅如此，吸附后的天然纤维素材料经过简单的酸处理，就能再生重复使用，工艺过程环保。 Natural cellulose materials, such as cotton, bamboo fiber, flax, etc., contain a variety of active groups on the surface, such as carboxyl, carbonyl, hydroxyl, etc., which can selectively absorb heavy metals such as lead, chromium, cadmium, iron, copper, and cobalt from the solution , so as to realize the purification of zinc bromide. Compared with the sublimation process, the natural cellulose material adsorption purification process consumes almost no energy and can achieve large-scale production; not only that, the absorbed natural cellulose material can be regenerated and reused after simple acid treatment, and the process is environmentally friendly.
发明内容 Contents of the invention
本发明提出一种电池级溴化锌的制备方法。本发明提出的制备方法是将锌粉置于去离子水中，滴加溴单质，搅拌24小时，过滤；将滤液稀释，与天然纤维材料混和，搅拌24小时，过滤，浓缩，得电池级溴化锌。其中锌粉与溴单质的摩尔比为1.2~1.6，锌粉与去离子水的固/液比为1～2 g/mL，天然纤维材料为棉花、竹纤维、亚麻中的任何一种，天然纤维材料与锌粉的重量比为10～50。本发明制备的溴化锌具有以下优点：（1）纯度高，大于99.99%；（2）工艺简单，适合于大规模生产；（3）原材料易得，生产成本低。本发明制备的溴化锌可广泛于高容量可充电池、高效率太阳能电池等工业领域。 The invention proposes a method for preparing battery-grade zinc bromide. The preparation method proposed by the present invention is to place zinc powder in deionized water, add bromine element dropwise, stir for 24 hours, and filter; dilute the filtrate, mix it with natural fiber materials, stir for 24 hours, filter, and concentrate to obtain battery-grade bromine zinc. Among them, the molar ratio of zinc powder to bromine element is 1.2~1.6, the solid/liquid ratio of zinc powder to deionized water is 1~2 g/mL, and the natural fiber material is any one of cotton, bamboo fiber, flax, natural The weight ratio of the fiber material to the zinc powder is 10-50. The zinc bromide prepared by the invention has the following advantages: (1) high purity, greater than 99.99%; (2) simple process, suitable for large-scale production; (3) easy to obtain raw materials, low production cost. The zinc bromide prepared by the invention can be widely used in high-capacity rechargeable batteries, high-efficiency solar cells and other industrial fields.
具体实施方式 Detailed ways
下面通过实施例进一步描述本发明 Further describe the present invention below by embodiment
实施例1Example 1
将1.6摩尔锌粉置于100mL去离子水中，滴加1摩尔溴单质，室温搅拌24小时，过滤；将滤液稀释至10升，与1200g棉花混和，室温搅拌24小时，过滤，浓缩，得电池级溴化锌，经检测熔点为394℃，纯度大于99.99%，杂质重金属总含量小于10ppm。 Put 1.6 moles of zinc powder in 100 mL of deionized water, add 1 mole of bromine dropwise, stir at room temperature for 24 hours, and filter; dilute the filtrate to 10 liters, mix with 1200 g of cotton, stir at room temperature for 24 hours, filter, and concentrate to obtain battery grade Zinc bromide has a detected melting point of 394°C, a purity of greater than 99.99%, and a total content of impurity heavy metals of less than 10ppm.
实施例2Example 2
将1.2摩尔锌粉置于100mL去离子水中，滴加1摩尔溴单质，室温搅拌24小时，过滤；将滤液稀释至10升，与1000g竹纤维混和，室温搅拌24小时，过滤，浓缩，得电池级溴化锌，经检测熔点为394℃，纯度大于99.99%，杂质重金属总含量小于10ppm。 Put 1.2 moles of zinc powder in 100 mL of deionized water, add 1 mole of bromine dropwise, stir at room temperature for 24 hours, and filter; dilute the filtrate to 10 liters, mix with 1000 g of bamboo fiber, stir at room temperature for 24 hours, filter, and concentrate to obtain a battery Grade zinc bromide, the detected melting point is 394°C, the purity is greater than 99.99%, and the total content of impurity heavy metals is less than 10ppm.
实施例3Example 3
将1.4摩尔锌粉置于150mL去离子水中，滴加1摩尔溴单质，室温搅拌24小时，过滤；将滤液稀释至10升，与1500g亚麻混和，室温搅拌24小时，过滤，浓缩，得电池级溴化锌，经检测熔点为394℃，纯度大于99.99%，杂质重金属总含量小于10ppm。 Put 1.4 moles of zinc powder in 150 mL of deionized water, add dropwise 1 mole of bromine, stir at room temperature for 24 hours, and filter; dilute the filtrate to 10 liters, mix with 1500 g of flax, stir at room temperature for 24 hours, filter, and concentrate to obtain battery grade Zinc bromide has a detected melting point of 394°C, a purity of greater than 99.99%, and a total content of impurity heavy metals of less than 10ppm.
实施例4Example 4
将1.3摩尔锌粉置于130mL去离子水中，滴加1摩尔溴单质，室温搅拌24小时，过滤；将滤液稀释至10升，与1000g竹纤维混和，室温搅拌24小时，过滤，浓缩，得电池级溴化锌，经检测熔点为394℃，纯度大于99.99%，杂质重金属总含量小于10ppm。 Put 1.3 moles of zinc powder in 130 mL of deionized water, add dropwise 1 mole of bromine, stir at room temperature for 24 hours, and filter; dilute the filtrate to 10 liters, mix with 1000 g of bamboo fiber, stir at room temperature for 24 hours, filter, and concentrate to obtain a battery Grade zinc bromide, the detected melting point is 394°C, the purity is greater than 99.99%, and the total content of impurity heavy metals is less than 10ppm.
实施例5Example 5
将1.5摩尔锌粉置于200mL去离子水中，滴加1摩尔溴单质，室温搅拌24小时，过滤；将滤液稀释至10升，与1800g棉花混和，室温搅拌24小时，过滤，浓缩，得电池级溴化锌，经检测熔点为394℃，纯度大于99.99%，杂质重金属总含量小于10ppm。 Put 1.5 moles of zinc powder in 200 mL of deionized water, add dropwise 1 mole of bromine, stir at room temperature for 24 hours, and filter; dilute the filtrate to 10 liters, mix with 1800 g of cotton, stir at room temperature for 24 hours, filter, and concentrate to obtain battery grade Zinc bromide has a detected melting point of 394°C, a purity of greater than 99.99%, and a total content of impurity heavy metals of less than 10ppm.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210150024.6A CN102659173B (en) | 2012-05-16 | 2012-05-16 | A kind of preparation method of battery-grade zinc bromide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210150024.6A CN102659173B (en) | 2012-05-16 | 2012-05-16 | A kind of preparation method of battery-grade zinc bromide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102659173A true CN102659173A (en) | 2012-09-12 |
| CN102659173B CN102659173B (en) | 2016-08-10 |
Family
ID=46768795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210150024.6A Expired - Fee Related CN102659173B (en) | 2012-05-16 | 2012-05-16 | A kind of preparation method of battery-grade zinc bromide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102659173B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061763A (en) * | 1990-11-27 | 1992-06-10 | 彭长 | A kind of production zinc chloride novel process |
| US6036937A (en) * | 1998-11-18 | 2000-03-14 | Tetra Technologies, Inc. | Method for producing zinc bromide |
| DE10053359A1 (en) * | 2000-10-27 | 2002-05-08 | Thueringisches Inst Textil | Cellulose fiber or film production with neutral adsorbent properties, for use e.g. in air filters, involves wet-spinning solution in aqueous tert. amine oxide containing cellulose and finely-divided neutral adsorber |
| CN101626980A (en) * | 2007-03-02 | 2010-01-13 | 雅宝公司 | The ultra-high purity zinc bromide and the quaternary ammonium bromides that are used for zinc-Zn-Br battery |
| CN102303897A (en) * | 2011-04-06 | 2012-01-04 | 冯若愚 | Method for preparing zinc chloride from chemical fiber slag |
-
2012
- 2012-05-16 CN CN201210150024.6A patent/CN102659173B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061763A (en) * | 1990-11-27 | 1992-06-10 | 彭长 | A kind of production zinc chloride novel process |
| US6036937A (en) * | 1998-11-18 | 2000-03-14 | Tetra Technologies, Inc. | Method for producing zinc bromide |
| DE10053359A1 (en) * | 2000-10-27 | 2002-05-08 | Thueringisches Inst Textil | Cellulose fiber or film production with neutral adsorbent properties, for use e.g. in air filters, involves wet-spinning solution in aqueous tert. amine oxide containing cellulose and finely-divided neutral adsorber |
| CN101626980A (en) * | 2007-03-02 | 2010-01-13 | 雅宝公司 | The ultra-high purity zinc bromide and the quaternary ammonium bromides that are used for zinc-Zn-Br battery |
| CN102303897A (en) * | 2011-04-06 | 2012-01-04 | 冯若愚 | Method for preparing zinc chloride from chemical fiber slag |
Non-Patent Citations (2)
| Title |
|---|
| 王焰新: ""去除废水中重金属的低成本吸附剂：生物质和地质材料的环境利用"", 《地学前缘（中国地质大学，北京）》 * |
| 黄敏文等: "《化学分析的样品处理》", 31 May 2007, 化学工业出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102659173B (en) | 2016-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107170967A (en) | Pre- intercalated layered barium oxide nano material of bivalent metal ion and its preparation method and application | |
| CN104016405B (en) | A kind of flower-shaped mesoporous titanium dioxide material and preparation method thereof and application | |
| CN103950992B (en) | The method of the transition metal oxide nano-slice of graphenic surface growing upright | |
| CN101235214A (en) | Organic ruthenium dyes and dye-sensitized solar cells | |
| CN102295602B (en) | Ionic liquid with esteryl imidazole group and preparation method and application thereof | |
| CN114497662B (en) | Application of multi-electron hexaazanaphthalene compound in aqueous flow battery | |
| CN101944396A (en) | Method for preparing porous mold charcoal/metal oxide composite material for super capacitor electrode | |
| Jia et al. | Enhanced performance of dye-sensitized solar cells with Y-shaped organic dyes containing di-anchoring groups | |
| CN103545524B (en) | Zinc-Polyaniline Cell and preparation method thereof | |
| CN101694813B (en) | Liquid crystal electrolyte solution for dye-sensitized nano film solar battery | |
| CN105293563A (en) | Zinc oxide nano-sheet cluster and preparation method thereof | |
| CN111584251A (en) | Duckweed-based carbon-coated metal oxide electrode material and preparation method thereof | |
| CN107381531A (en) | A kind of preparation method of difluorophosphate | |
| CN102250484A (en) | Carbazolyl organic dye used for dye-sensitized solar cells and preparation method thereof | |
| CN107045948A (en) | NaxMnO2Positive electrode, preparation method and applications | |
| Xie et al. | Advances and prospects of porphyrin derivatives in the energy field | |
| CN105977050B (en) | A kind of preparation method of carbon nanotubes/metal zirconium organic framework material for ultracapacitor | |
| CN103145761B (en) | Utilize the method for recrystallization method purification Ruthenium complex crude product | |
| CN115583638A (en) | A kind of purification method of crude lithium phosphate | |
| CN110183624A (en) | A kind of preparation method of hyperbranched carbazole triphen amine conjugated polymer electrolyte cathode interface layer | |
| CN105226262A (en) | A kind of preparation method of super long titanium dioxide nano wire | |
| CN102659173B (en) | A kind of preparation method of battery-grade zinc bromide | |
| CN102502792B (en) | Preparation method of spherical SnS nanometer crystals | |
| CN104716343B (en) | A kind of high-performance is combined carbon felt | |
| CN105694525B (en) | Axial-coordination self-assembly metalloporphyrin dye sensitizer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160810 Termination date: 20190516 |