JP2019079789A - Preparing method of electrode for vanadium redox battery - Google Patents
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- JP2019079789A JP2019079789A JP2018181203A JP2018181203A JP2019079789A JP 2019079789 A JP2019079789 A JP 2019079789A JP 2018181203 A JP2018181203 A JP 2018181203A JP 2018181203 A JP2018181203 A JP 2018181203A JP 2019079789 A JP2019079789 A JP 2019079789A
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- carbon nanotubes
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- vinyl acetate
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 35
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 42
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 23
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 21
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000005187 foaming Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 239000004088 foaming agent Substances 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000002048 multi walled nanotube Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 6
- -1 azo compound Chemical class 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 229920000049 Carbon (fiber) Polymers 0.000 description 8
- 239000004917 carbon fiber Substances 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- 239000004604 Blowing Agent Substances 0.000 description 6
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004176 ammonification Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
Classifications
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
Description
本発明は、バナジウムレドックス電池の電極材料を調製する方法、特に、バナジウムレドックス電池用の電極を調製する方法に関する。 The present invention relates to a method of preparing an electrode material of a vanadium redox battery, in particular to a method of preparing an electrode for a vanadium redox battery.
バナジウムレドックス電池は、基本的に、エンドプレート、バイポーラプレート、電極およびダイヤフラムなどの主要材料から成る大規模なエネルギー貯蔵に適した比較的クリーンな電池システムである。バナジウムレドックス電池の最も重要な構成要素の１つとして、電極およびその関連特性（コストおよび処理技術などを含む）は、バナジウムレドックス電池システムの研究開発にとって重要な側面となっている。バナジウム電極の研究開発において、研究者らは、金属材料、グラファイト板、炭素電極の詳細な調査を行い、現在ではポリアクリロニトリル炭素繊維フェルトがバナジウムレドックス電池に用いられている電極材料の中で最も一般的であるが、バナジウムレドックス電池の要求を満たすことができないことを発見した。その主な理由は以下の通りである。（１）現在市販されている炭素繊維フェルトはバナジウムレドックス電池用に特別に製造されていないので、電池におけるその活性は不十分である。使用前に、グラファイトフェルトの表面を処理してその性能を改善しなければならない。グラファイトフェルトの一般的な処理方法としては、金属イオン改質、酸処理、熱処理、アンモニア化処理、電気化学的処理および総合的な処理などがある。比較的熟慮された処理方法は、酸処理のような工業生産を実現することができるが、深刻な環境汚染、複雑な操作、熱処理中の高エネルギー消費のような不利点がある。これらの処理方法は、炭素繊維フェルトの活性を高める一方で、炭素繊維フェルトの表面上のグラファイト層の構造を損なう可能性があり、その結果、炭素繊維フェルトの導電性を低下させる可能性がある。また、金属改質により、バナジウムレドックス電池の性能に好ましくない不純物がいくらか導入される場合があり、プラズマ処理やアンモニア化処理が工業生産を実現するのは難しい。（２）炭素繊維フェルトは高価であり、使用前に活性化処理が必要となり、大きなコストアップにつながる。バナジウムレドックス電池の開発において、価格は市場で販売できるかどうかを決定する重要な要因である。したがって、価格を下げることは効果的にバナジウムレドックス電池の開発を促進する。 Vanadium redox batteries are basically relatively clean battery systems suitable for large-scale energy storage consisting of main materials such as end plates, bipolar plates, electrodes and diaphragms. As one of the most important components of vanadium redox batteries, the electrodes and their associated characteristics (including cost and processing technology etc.) are important aspects for research and development of vanadium redox battery systems. In the research and development of vanadium electrodes, researchers conducted a detailed investigation of metal materials, graphite plates, and carbon electrodes, and polyacrylonitrile carbon fiber felt is currently the most common electrode material used in vanadium redox batteries. It has been discovered that the requirements of vanadium redox batteries can not be met. The main reasons are as follows. (1) Since carbon fiber felts currently marketed are not specially manufactured for vanadium redox batteries, their activity in batteries is insufficient. Before use, the surface of the graphite felt must be treated to improve its performance. Typical methods for treating graphite felt include metal ion modification, acid treatment, heat treatment, ammonification treatment, electrochemical treatment and comprehensive treatment. Relatively considered treatment methods can realize industrial production such as acid treatment, but have disadvantages such as severe environmental pollution, complicated operation, high energy consumption during heat treatment. While these treatments increase the activity of the carbon fiber felt, they can damage the structure of the graphite layer on the surface of the carbon fiber felt, and as a result, can reduce the conductivity of the carbon fiber felt. . Also, metal modification may introduce some impurities that are not desirable for the performance of vanadium redox batteries, and it is difficult for plasma treatment and ammonification treatment to realize industrial production. (2) Carbon fiber felt is expensive and requires activation treatment before use, leading to significant cost increase. In the development of vanadium redox batteries, price is an important factor in determining whether it can be marketed. Thus, lowering the price effectively promotes the development of vanadium redox batteries.
本発明により解決すべき技術的課題は、バナジウムレドックス電池用の電極を低コストで、さらなる後処理なしに調製する方法を提供することである。 The technical problem to be solved by the present invention is to provide a method for preparing an electrode for a vanadium redox battery at low cost without further aftertreatment.
本発明の技術的課題を解決するための技術スキームは、バナジウムレドックス電池用の電極の調製方法において：
（ａ）カーボンナノチューブの前処理ステップであって：多層カーボンナノチューブを選択して、質量％で５％の過酸化水素中に浸漬し、常温で５〜８時間超音波処理した後、遠心分離処理を行い；続いてカーボンナノチューブを蒸留水で２〜３回浸出させた後、乾燥させ、濃硫酸と濃硝酸との混酸溶液に１：２〜５の固液体積比で乾燥させたカーボンナノチューブを浸漬した後、常温で６〜１０時間超音波処理を行い、固液混合物の体積の３〜５倍の体積の蒸留水で希釈し、カーボンナノチューブが完全に沈殿するまで静置し、固液分離を行い；
上記の「固液混合物の体積の３〜５倍の体積の蒸留水で希釈し、カーボンナノチューブが完全に沈殿するまで静置し、固液分離を行う」操作を２〜３回繰り返し、そしてカーボンナノチューブを７０〜９０℃で乾燥させるステップと；
（ｂ）酸化バナジウムゲルの調製ステップであって：高純度の五酸化バナジウムを準備して９８％の濃度の硫酸に１：１〜３の固液体積比で添加した後、濃硫酸の５〜１０倍の体積の蒸留水を加え、系が室温に冷却されるまで１０〜３０ｒｐｓの回転速度で撹拌し、５０〜６５℃で乾燥させて、粉砕するステップと；
（ｃ）エチレン酢酸ビニル共重合体のカーボンナノチューブ等との混合ステップであって：酢酸ビニル含有率が２０％未満のエチレン酢酸ビニル共重合体を選択し、エチレン酢酸ビニル共重合体：カーボンナノチューブ：酸化バナジウムゲル：発泡剤を１００：５０〜７０：１〜３：５〜１０の質量比に従ってそれぞれ準備し、カーボンナノチューブと酸化バナジウムゲルと発泡剤とを均一に混合してカーボンナノチューブ混合物を得、エチレン酢酸ビニル共重合体とカーボンナノチューブ混合物とを順次添加して１５〜３０分間精製し、その後ツインローラを通過させてチップ化および破砕するステップと；
（ｄ）エチレン酢酸ビニル共重合体とカーボンナノチューブとの混合物の発泡ステップであって：ステップ（ｃ）で調製された混合物を適量採取し、組み立てられたバナジウムレドックス電池に必要な電極の大きさと厚さを有する型に入れ、１６０〜１９０℃で１５〜３０分間発泡させ、室温になるまで冷却し、室温で２４〜３６時間静置し、生成物を取り出して調製するステップと；
を含む方法である。
The technical scheme for solving the technical problem of the present invention is a method of preparing an electrode for vanadium redox battery:
(A) A pretreatment step of carbon nanotubes: Multi-wall carbon nanotubes are selected, immersed in 5% by weight of hydrogen peroxide, ultrasonicated at normal temperature for 5 to 8 hours, and then centrifuged Subsequently, the carbon nanotubes are leached with distilled water two to three times, dried, and dried in a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid at a solid-liquid volume ratio of 1: 2 to 5; After immersion, sonicate at room temperature for 6 to 10 hours, dilute with distilled water 3 to 5 times the volume of the solid-liquid mixture, and allow to settle completely until carbon nanotubes are precipitated, solid-liquid separation Do;
Repeat the above operation “dilute with 3 to 5 times the volume of the solid-liquid mixture, leave it until the carbon nanotubes are completely precipitated, and perform solid-liquid separation” a couple of times, and carbon Drying the nanotubes at 70-90 ° C .;
(B) Preparation step of vanadium oxide gel: after preparing vanadium pentoxide of high purity and adding it to sulfuric acid of 98% concentration at a solid-liquid volume ratio of 1: 1 to 3, then 5 to 5 of concentrated sulfuric acid Adding 10 volumes of distilled water, stirring at a rotational speed of 10-30 rps until the system is cooled to room temperature, drying at 50-65 ° C. and grinding;
(C) mixing the ethylene vinyl acetate copolymer with carbon nanotubes etc .: selecting an ethylene vinyl acetate copolymer having a vinyl acetate content of less than 20%; ethylene vinyl acetate copolymer: carbon nanotubes: Vanadium oxide gel: a foaming agent is prepared according to a mass ratio of 100: 50 to 70: 1 to 3: 5 to 10, respectively, and the carbon nanotube, the vanadium oxide gel and the foaming agent are uniformly mixed to obtain a carbon nanotube mixture Ethylene-vinyl acetate copolymer and a mixture of carbon nanotubes are sequentially added and purified for 15 to 30 minutes, and then passed through a twin roller for chipping and crushing;
(D) foaming step of a mixture of ethylene vinyl acetate copolymer and carbon nanotubes: taking an appropriate amount of the mixture prepared in step (c), size and thickness of electrode required for assembled vanadium redox battery Putting in molds, foaming at 160 to 190 ° C. for 15 to 30 minutes, cooling to room temperature, standing at room temperature for 24 to 36 hours, taking out the product and preparing;
Method.
さらに、ステップ（ａ）における多層カーボンナノチューブの長さ−直径比は、５０〜８０である。 Furthermore, the length-diameter ratio of the multi-walled carbon nanotube in step (a) is 50-80.
さらに、ステップ（ａ）における多層カーボンナノチューブの過酸化水素に対する固液体積比は、１：２〜５の範囲である。 Furthermore, the solid-liquid volume ratio of multi-walled carbon nanotubes to hydrogen peroxide in step (a) is in the range of 1: 2-5.
さらに、ステップ（ａ）における濃硫酸と濃硝酸との混酸溶液において、濃硫酸の質量分率は９８％であり、濃硝酸の質量分率は６０％である。 Furthermore, in the mixed acid solution of concentrated sulfuric acid and concentrated nitric acid in step (a), the mass fraction of concentrated sulfuric acid is 98%, and the mass fraction of concentrated nitric acid is 60%.
さらに、ステップ（ａ）における濃硫酸の濃硝酸に対する体積比は３：１である。 Furthermore, the volume ratio of concentrated sulfuric acid to concentrated nitric acid in step (a) is 3: 1.
さらに、ステップ（ｃ）における発泡剤は、アゾ化合物発泡剤またはスルホニルヒドラジド化合物発泡剤である。 Furthermore, the blowing agent in step (c) is an azo compound blowing agent or a sulfonyl hydrazide compound blowing agent.
さらに、ステップ（ｃ）におけるチップ化および破砕に使用されるツインローラの上部ローラの温度は７０〜９０℃であり、ローラフレーム間の距離は１〜２ｍｍである。 Furthermore, the temperature of the upper roller of the twin roller used for chipping and crushing in step (c) is 70 to 90 ° C., and the distance between the roller frames is 1 to 2 mm.
本発明の有益な効果は、該方法の非常に明白な技術的利点にある：（１）低コストかつ簡単な調製方法である。該方法は、現在の炭素繊維フェルトで活性化された電極と比較して、製造後の電池の連続使用が可能であり、簡単な製造および低エネルギー消費という利点がある。従来のスキームでは、炭素繊維フェルトの黒鉛化プロセスを制御することは非常に困難であり、反応温度および雰囲気条件は非常に厳しく、二次活性化処理はそれに応じてコストおよび環境汚染を増大させる。（２）処方および官能基は、バナジウムレドックス電池の異なる要件に従って容易に調整される：本発明によって提供される方法におけるカーボンナノチューブおよび酸化バナジウムは、グラフェン、酸化ビスマスなどの他の導電性物質で置き換えることができ、処方およびマトリックス材料は、オンデマンドでの調製を実現するために必要に応じて直接置き換えることができる。（３）導入される活性官能基の量は多く、制御が容易である。（４）調製された生成物の導電性を、容易に制御することができる。本発明は、バナジウムレドックス電池用の電極の調製に特に適している。 The beneficial effects of the invention lie in the very obvious technical advantages of the method: (1) low cost and simple preparation methods. The method allows continuous use of the battery after manufacture as compared to current carbon fiber felt activated electrodes, and has the advantage of simple manufacture and low energy consumption. In the conventional scheme, it is very difficult to control the graphitization process of carbon fiber felt, the reaction temperature and atmosphere conditions are very strict, and the secondary activation treatment correspondingly increases cost and environmental pollution. (2) Formulation and functional groups are easily adjusted according to the different requirements of vanadium redox batteries: carbon nanotubes and vanadium oxide in the method provided by the present invention are replaced by other conductive materials such as graphene, bismuth oxide The formulation and matrix material can be directly replaced as needed to achieve on-demand preparation. (3) The amount of active functional groups introduced is large and easy to control. (4) The conductivity of the prepared product can be easily controlled. The invention is particularly suitable for the preparation of electrodes for vanadium redox batteries.
バナジウムレドックス電池用の電極の調製方法は：
（ａ）カーボンナノチューブの前処理ステップであって：多層カーボンナノチューブを選択して、質量％で５％の過酸化水素中に浸漬し、常温で５〜８時間超音波処理した後、遠心分離処理を行い；続いてカーボンナノチューブを蒸留水で２〜３回浸出させた後、乾燥させ、濃硫酸と濃硝酸との混酸溶液に固液体積比１：２〜５で乾燥させたカーボンナノチューブを浸漬した後、常温で６〜１０時間超音波処理を行い、固液混合物の体積の３〜５倍の体積の蒸留水で希釈し、カーボンナノチューブが完全に沈殿するまで静置し、固液分離を行い；上記の「固液混合物の体積の３〜５倍の体積の蒸留水で希釈し、カーボンナノチューブが完全に沈殿するまで静置し、固液分離を行う」操作を２〜３回繰り返し、そしてカーボンナノチューブを７０〜９０℃で乾燥させるステップと；（ｂ）酸化バナジウムゲルの調製ステップであって：高純度の五酸化バナジウムを準備して９８％の濃度の硫酸に固液体積比１：１〜３で添加した後、濃硫酸の５〜１０倍の体積の蒸留水を加え、系が室温に冷却されるまで１０〜３０ｒｐｓの回転速度で撹拌し、５０〜６５℃で乾燥させ、粉砕するステップと；（ｃ）エチレン酢酸ビニル共重合体のカーボンナノチューブ等との混合ステップであって：酢酸ビニル含有率が２０％未満のエチレン酢酸ビニル共重合体を選択し、エチレン酢酸ビニル共重合体：カーボンナノチューブ：酸化バナジウムゲル：発泡剤を１００：５０〜７０：１〜３：５〜１０の質量比に従ってそれぞれ準備し、まずカーボンナノチューブと酸化バナジウムゲルと発泡剤とを均一に混合してカーボンナノチューブ混合物を得、エチレン酢酸ビニル共重合体とカーボンナノチューブ混合物とを順次添加して１５〜３０分間精製し、その後ツインローラを通過させてチップ化および破砕するステップと；（ｄ）エチレン酢酸ビニル共重合体とカーボンナノチューブとの混合物の発泡ステップであって：ステップ（ｃ）で調製された混合物を適量採取し、組み立てられたバナジウムレドックス電池に必要な電極の大きさと厚さを有する型に入れ、１６０〜１９０℃で１５〜３０分間発泡させ、室温になるまで冷却し、室温で２４〜３６時間静置し、生成物を取り出して調製するステップとを含む。
The preparation method of the electrode for vanadium redox battery is:
(A) A pretreatment step of carbon nanotubes: Multi-wall carbon nanotubes are selected, immersed in 5% by weight of hydrogen peroxide, ultrasonicated at normal temperature for 5 to 8 hours, and then centrifuged Subsequently, the carbon nanotubes are leached with distilled water two or three times and then dried, and the carbon nanotubes dried at a solid-liquid volume ratio of 1: 2 to 5 are dipped in a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid. Then, sonicate at room temperature for 6 to 10 hours, dilute with distilled water 3 to 5 times the volume of the solid-liquid mixture, and allow to settle completely until carbon nanotubes are precipitated. Perform the above-mentioned operation “dilute with 3 to 5 times the volume of the solid-liquid mixture, leave it until the carbon nanotubes are completely precipitated, and perform solid-liquid separation” 2-3 times. And 7 carbon nanotubes And (b) preparing vanadium oxide gel: adding highly pure vanadium pentoxide and adding it to sulfuric acid at 98% concentration by volume ratio of 1: 1 to 1: 3. Then, add 5 to 10 volumes of distilled water of concentrated sulfuric acid, stir at a rotational speed of 10 to 30 rps until the system is cooled to room temperature, dry at 50 to 65 ° C., and grind; c) mixing step of ethylene vinyl acetate copolymer with carbon nanotubes etc .: selecting ethylene vinyl acetate copolymer having vinyl acetate content less than 20%, ethylene vinyl acetate copolymer: carbon nanotube: oxidation Vanadium gel: A foaming agent is prepared respectively according to a mass ratio of 100: 50 to 70: 1 to 3: 5 to 10, and first, carbon nanotubes, vanadium oxide gel and the foaming agent are equalized. Obtaining a mixture of carbon nanotubes in the mixture, sequentially adding ethylene vinyl acetate copolymer and the mixture of carbon nanotubes, purifying for 15 to 30 minutes, and then passing through a twin roller for chipping and crushing; B) foaming step of a mixture of ethylene vinyl acetate copolymer and carbon nanotubes: taking an appropriate amount of the mixture prepared in step (c) to obtain the size and thickness of the electrode necessary for the assembled vanadium redox battery Placing in a mold, foaming at 160-190 ° C. for 15-30 minutes, cooling to room temperature, standing at room temperature for 24-36 hours, removing the product and preparing.
エチレン酢酸ビニル共重合体は、ＥＶＡとしても知られている。一般に、市販されているエチレン酢酸ビニル共重合体は、要件を満たすことができる酢酸ビニル含有率が２０％未満である。実際の製造では、精製および最適化のために、以下のスキームが提供される：ステップ（ａ）における多層カーボンナノチューブの長さ−直径比は５０〜８０であり；ステップ（ａ）における多層カーボンナノチューブの過酸化水素に対する固液体積比は、１：２〜５の範囲である。濃硫酸と濃硝酸との混酸溶液では、濃硫酸の質量分率は９８％であり、濃硝酸の質量分率は６０％である。また、ステップ（ａ）における濃硫酸の濃硝酸に対する体積比は、好ましくは、３：１である。ステップ（ｃ）における発泡剤は、好ましくは、アゾ化合物発泡剤またはスルホニルヒドラジド化合物発泡剤である。さらに、ステップ（ｃ）におけるチップ化および破砕に使用されるツインローラの上部ローラの温度は７０〜９０℃であり、ローラフレーム間の距離は１〜２ｍｍである。 Ethylene vinyl acetate copolymers are also known as EVA. Generally, commercially available ethylene vinyl acetate copolymers have a vinyl acetate content that can meet the requirements is less than 20%. In actual production, the following scheme is provided for purification and optimization: length-diameter ratio of multi-walled carbon nanotubes in step (a) is 50-80; multi-walled carbon nanotubes in step (a) The solid-liquid volume ratio of hydrogen peroxide to hydrogen peroxide is in the range of 1: 2 to 5. In the mixed acid solution of concentrated sulfuric acid and concentrated nitric acid, the mass fraction of concentrated sulfuric acid is 98%, and the mass fraction of concentrated nitric acid is 60%. Also, the volume ratio of concentrated sulfuric acid to concentrated nitric acid in step (a) is preferably 3: 1. The blowing agent in step (c) is preferably an azo compound blowing agent or a sulfonyl hydrazide compound blowing agent. Furthermore, the temperature of the upper roller of the twin roller used for chipping and crushing in step (c) is 70 to 90 ° C., and the distance between the roller frames is 1 to 2 mm.
実施例１
ステップ（ａ）に従って処理したカーボンナノチューブ５０ｇとステップ（ｂ）で得られたバナジウム酸化ゲル１ｇとアゾ化合物発泡剤５ｇを準備し、均一に混合し、ツインローラが７０℃で保持されローラフレーム間の距離が１ｍｍであるときに、１００ｇのＥＶＡの存在下で３分間精製する。次に、カーボンナノチューブ混合物を添加し、１５分間精製し、精製した混合物を粉砕して型に入れ、１６５℃で２５分間発泡させ、２４時間静置して冷却すると、組み立てられたバナジウムレドックス電池は、電流効率が９０．１％、電圧効率が８５．４％であった。
Example 1
Prepare 50 g of carbon nanotubes treated according to step (a), 1 g of vanadium oxide gel obtained in step (b), and 5 g of azo compound foaming agent, mix uniformly, and maintain twin rollers at 70 ° C. When the distance is 1 mm, purify for 3 minutes in the presence of 100 g of EVA. The carbon nanotube mixture is then added, the mixture is purified for 15 minutes, and the purified mixture is crushed into molds, allowed to foam at 165 ° C. for 25 minutes, allowed to stand for 24 hours and allowed to cool, the assembled vanadium redox battery The current efficiency was 90.1% and the voltage efficiency was 85.4%.
実施例２
ステップ（ａ）に従って処理したカーボンナノチューブ６０ｇとステップ（ｂ）で得られたバナジウム酸化ゲル１ｇとアゾ化合物発泡剤８ｇを準備し、均一に混合し、ツインローラが８０℃で保持されローラフレーム間の距離が１．２ｍｍであるときに、１００ｇのＥＶＡの存在下で３分間精製する。次に、カーボンナノチューブ混合物を添加し、１７分間精製し、精製した混合物を粉砕して型に入れ、１７０℃で２５分間発泡させ、３０時間静置して冷却すると、組み立てられたバナジウムレドックス電池は、電流効率が９１．３％、電圧効率が８６．４％であった。
Example 2
60 g of carbon nanotubes treated according to step (a), 1 g of vanadium oxide gel obtained in step (b) and 8 g of azo compound foaming agent are prepared and mixed uniformly, and twin rollers are held at 80 ° C. Purify for 3 minutes in the presence of 100 g of EVA when the distance is 1.2 mm. The carbon nanotube mixture is then added, purified for 17 minutes, and the purified mixture is crushed into molds, allowed to foam at 170 ° C. for 25 minutes, allowed to stand for 30 hours and allowed to cool, the assembled vanadium redox battery The current efficiency was 91.3% and the voltage efficiency was 86.4%.
実施例３
ステップ（ａ）に従って処理したカーボンナノチューブ７０ｇとステップ（ｂ）で得られたバナジウム酸化ゲル１ｇとアゾ化合物発泡剤９ｇを準備し、均一に混合し、ツインローラが９０℃で保持されローラフレーム間の距離が１．５ｍｍであるときに、１００ｇのＥＶＡの存在下で３分間精製する。次に、カーボンナノチューブ混合物を添加し、２７分間精製し、精製した混合物を粉砕して型に入れ、１８０℃で１５分間発泡させ、３６時間静置して冷却すると、組み立てられたバナジウムレドックス電池は、電流効率が９２．３％、電圧効率が８６．９％であった。
Example 3
70 g of carbon nanotubes treated according to step (a), 1 g of vanadium oxide gel obtained in step (b) and 9 g of azo compound foaming agent are prepared and mixed uniformly, twin rollers are held at 90 ° C. Purify for 3 minutes in the presence of 100 g of EVA when the distance is 1.5 mm. The carbon nanotube mixture is then added, purified for 27 minutes, and the purified mixture is crushed into molds, allowed to foam at 180 ° C. for 15 minutes, allowed to stand for 36 hours and allowed to cool, the assembled vanadium redox battery The current efficiency was 92.3% and the voltage efficiency was 86.9%.
上記の実施例により調製されたバナジウムレドックス電池用の電極は、低コストかつ簡単な調製方法などの明らかな技術的利点を有する。 The electrodes for vanadium redox batteries prepared according to the above examples have obvious technical advantages such as low cost and simple preparation methods.
Claims (7)
（ａ）カーボンナノチューブの前処理ステップであって：多層カーボンナノチューブを選択して、質量％で５％の過酸化水素中に浸漬し、常温で５〜８時間超音波処理した後、遠心分離処理を行い；続いて前記カーボンナノチューブを蒸留水で２〜３回浸出させた後、乾燥させ、濃硫酸と濃硝酸との混酸溶液に１：２〜５の固液体積比で乾燥させたカーボンナノチューブを浸漬した後、常温で６〜１０時間超音波処理を行い、固液混合物の体積の３〜５倍の体積の蒸留水で希釈し、前記カーボンナノチューブが完全に沈殿するまで静置し、固液分離を行い；
上記の「固液混合物の体積の３〜５倍の体積の蒸留水で希釈し、カーボンナノチューブが完全に沈殿するまで静置し、固液分離を行う」操作を２〜３回繰り返し、そして前記カーボンナノチューブを７０〜９０℃で乾燥させるステップと；
（ｂ）酸化バナジウムゲルの調製ステップであって：高純度の五酸化バナジウムを準備して９８％の濃度の硫酸に１：１〜３の固液体積比で添加した後、前記濃硫酸の５〜１０倍の体積の蒸留水を加え、系が室温に冷却されるまで１０〜３０ｒｐｓの回転速度で撹拌し、５０〜６５℃で乾燥させて、粉砕するステップと；
（ｃ）エチレン酢酸ビニル共重合体の前記カーボンナノチューブ等との混合ステップであって：酢酸ビニル含有率が２０％未満のエチレン酢酸ビニル共重合体を選択し、エチレン酢酸ビニル共重合体：カーボンナノチューブ：酸化バナジウムゲル：発泡剤を１００：５０〜７０：１〜３：５〜１０の質量比に従ってそれぞれ準備し、まず前記カーボンナノチューブと前記酸化バナジウムゲルと前記発泡剤とを均一に混合してカーボンナノチューブ混合物を得、エチレン酢酸ビニル共重合体と前記カーボンナノチューブ混合物とを順次添加して１５〜３０分間精製し、その後ツインローラを通過させてチップ化および破砕するステップと、
（ｄ）エチレン酢酸ビニル共重合体と前記カーボンナノチューブとの混合物の発泡ステップであって：ステップ（ｃ）で調製された前記混合物を適量採取し、前記組み立てられたバナジウムレドックス電池に必要な電極の大きさと厚さを有する型に入れ、１６０〜１９０℃で１５〜３０分間発泡させ、室温になるまで冷却し、室温で２４〜３６時間静置し、生成物を取り出して調製するステップと、
を含む、調製方法。 In the preparation method of electrode for vanadium redox battery:
(A) A pretreatment step of carbon nanotubes: Multi-wall carbon nanotubes are selected, immersed in 5% by weight of hydrogen peroxide, ultrasonicated at normal temperature for 5 to 8 hours, and then centrifuged Subsequently, the carbon nanotubes are leached with distilled water two to three times, dried, and dried in a mixed acid solution of concentrated sulfuric acid and concentrated nitric acid at a solid-liquid volume ratio of 1: 2 to 5 Soak the plate, sonicate at room temperature for 6 to 10 hours, dilute with distilled water 3 to 5 times the volume of the solid-liquid mixture, and let it stand until the carbon nanotubes are completely precipitated, Perform liquid separation;
Repeat the above operation “dilute with 3 to 5 times the volume of the solid-liquid mixture, leave it until the carbon nanotubes are completely precipitated, and perform solid-liquid separation” a few times, and Drying the carbon nanotubes at 70-90 ° C .;
(B) Preparation step of vanadium oxide gel: after preparing highly pure vanadium pentoxide and adding it to sulfuric acid of 98% concentration at a solid-liquid volume ratio of 1: 1 to 3, 5 of the concentrated sulfuric acid Adding ~ 10 volumes of distilled water, stirring at a rotational speed of 10-30 rps until the system is cooled to room temperature, drying at 50-65 ° C. and grinding;
(C) mixing the ethylene-vinyl acetate copolymer with the carbon nanotubes etc .: selecting an ethylene-vinyl acetate copolymer having a vinyl acetate content of less than 20%; ethylene-vinyl acetate copolymer: carbon nanotubes : Vanadium oxide gel: A foaming agent is prepared according to a mass ratio of 100: 50 to 70: 1 to 3: 5 to 10, first, the carbon nanotube, the vanadium oxide gel and the foaming agent are uniformly mixed to obtain carbon Obtaining a nanotube mixture, sequentially adding an ethylene-vinyl acetate copolymer and the carbon nanotube mixture, purifying for 15 to 30 minutes, and then passing through a twin roller for chipping and crushing;
(D) A foaming step of a mixture of ethylene vinyl acetate copolymer and the carbon nanotube: an appropriate amount of the mixture prepared in step (c) is collected to obtain an electrode necessary for the assembled vanadium redox battery Put in a mold having a size and thickness, foam at 160 to 190 ° C. for 15 to 30 minutes, cool to room temperature, stand at room temperature for 24 to 36 hours, take out and prepare a product,
A method of preparation, including
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| CN114094120B (en) * | 2021-11-23 | 2023-10-27 | 成都先进金属材料产业技术研究院股份有限公司 | Integrated graphite electrode for vanadium battery and vanadium battery |
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| JP6700360B2 (en) | 2020-05-27 |
| CN107623132A (en) | 2018-01-23 |
| CN107623132B (en) | 2020-05-12 |
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