CN1268550C - Process for preparing layered manganese dioxide with big and stable layer space - Google Patents
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000011229 interlayer Substances 0.000 claims abstract description 17
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 20
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 8
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical group Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 8
- 239000011565 manganese chloride Substances 0.000 claims description 8
- 235000002867 manganese chloride Nutrition 0.000 claims description 8
- 229940099607 manganese chloride Drugs 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 2
- XNZJTLSFOOXUAS-UHFFFAOYSA-N cobalt hydrochloride Chemical compound Cl.[Co] XNZJTLSFOOXUAS-UHFFFAOYSA-N 0.000 claims 2
- FBAFATDZDUQKNH-UHFFFAOYSA-N iron;hydrochloride Chemical compound Cl.[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-N 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000003381 stabilizer Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 6
- 229940097267 cobaltous chloride Drugs 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940045032 cobaltous nitrate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Abstract
本发明公开了一种层间距大且稳定的层状二氧化锰的制备方法，其特征是：以水溶性二价锰盐和无机碱为原料，以阳离子型表面活性剂为模板，以水溶性二价钴盐或三价铁盐为结构稳定剂制得，所制得的层状二氧化锰具有结构稳定且层间距大(1.5～3.5nm)，可用作电池和超级电容器电极材料，高效催化材料及吸附材料等。The invention discloses a preparation method of layered manganese dioxide with large and stable interlayer spacing, which is characterized in that: water-soluble divalent manganese salt and inorganic alkali are used as raw materials, cationic surfactant is used as template, and water-soluble Divalent cobalt salt or ferric salt is used as a structural stabilizer. The obtained layered manganese dioxide has a stable structure and a large interlayer distance (1.5-3.5nm). It can be used as an electrode material for batteries and supercapacitors, and is highly efficient. Catalytic materials and adsorption materials, etc.
Description
技术领域technical field
本发明涉及一种层状二氧化锰的制备方法，特别涉及一种层间距大且稳定的层状二氧化锰的制备方法。The invention relates to a method for preparing layered manganese dioxide, in particular to a method for preparing layered manganese dioxide with large and stable layer spacing.
背景技术Background technique
层状二氧化锰具有价格低廉、低毒、较大的比表面积及优异的化学和电化学性能等优点，是能源、化工等领域的一种重要的原料。其被广泛用于锌锰、可充电碱锰、锂锰和锂离子电池的正极材料和超级电容器的电极材料；而在化学工业中，其也可用于高效催化材料及吸附材料。Layered manganese dioxide has the advantages of low price, low toxicity, large specific surface area and excellent chemical and electrochemical properties. It is an important raw material in the fields of energy and chemical industry. It is widely used in positive electrode materials of zinc-manganese, rechargeable alkaline manganese, lithium manganese and lithium-ion batteries and electrode materials of supercapacitors; in the chemical industry, it can also be used as high-efficiency catalytic materials and adsorption materials.
目前制备层状二氧化锰的方法包括：高锰酸钾还原法、氢氧化锰氧化法和溶胶凝胶法等。前两种方法制得的层状二氧化锰的层间距较小(约为0.7nm)，其比表面积也不够大且层间距不稳定，易受层间介质和温度的影响，而溶胶凝胶法制得的层状二氧化锰的层间距虽然较大，但其制备工艺较复杂。The current methods for preparing layered manganese dioxide include potassium permanganate reduction method, manganese hydroxide oxidation method and sol-gel method. The interlayer spacing of the layered manganese dioxide prepared by the first two methods is small (about 0.7nm), its specific surface area is not large enough and the interlayer spacing is unstable, and it is easily affected by the interlayer medium and temperature, while the sol-gel Although the interlayer spacing of the layered manganese dioxide prepared by the method is relatively large, its preparation process is relatively complicated.
发明内容Contents of the invention
本发明的目的在于，提供一种层间距大且稳定的层状二氧化锰的制备方法。The object of the present invention is to provide a method for preparing layered manganese dioxide with large and stable interlayer spacing.
本发明的制备方法不同于传统的化学方法，而采用模板自组装方法，其特征特征是以水溶性二价锰盐和无机碱为原料，以阳离子型表面活性剂为模板，以水溶性二价钴盐或三价铁盐为结构稳定剂，通过模板自组装方法制得结构稳定且具有大层间距(1.5～3.5nm)的层状二氧化锰。其制备方法包括如下步骤：The preparation method of the present invention is different from the traditional chemical method, but adopts the template self-assembly method, and its characteristic feature is to use water-soluble divalent manganese salt and inorganic alkali as raw materials, use cationic surfactant as template, and use water-soluble divalent manganese salt as raw material Cobalt salt or ferric salt is used as a structure stabilizer, and layered manganese dioxide with stable structure and large interlayer distance (1.5-3.5nm) is prepared by template self-assembly method. Its preparation method comprises the following steps:
将水溶性二价锰盐与二价钴盐或三价铁盐按摩尔比1∶0.1～0.6溶于去离子水中，在搅拌下，将上述溶液逐渐加入到无机碱与阳离子型表面活性剂的水溶液中，控制反应温度为10～70℃，搅拌反应1～4小时，然后升温至100℃，继续老化反应8～168小时，过滤、水洗，将得到的固体物置于70～80℃烘干，即得层状二氧化锰粉末。Dissolve water-soluble divalent manganese salt and divalent cobalt salt or ferric salt in deionized water at a molar ratio of 1:0.1 to 0.6, and gradually add the above solution to the mixture of inorganic alkali and cationic surfactant under stirring. In the aqueous solution, control the reaction temperature at 10-70°C, stir the reaction for 1-4 hours, then raise the temperature to 100°C, continue the aging reaction for 8-168 hours, filter, wash with water, and dry the obtained solid at 70-80°C. The layered manganese dioxide powder is obtained.
其中：所述的阳离子型表面活性剂用量为0.1～5wt％；阳离子型表面活性剂与二价锰盐的摩尔比为2～6∶1；无机碱与二价锰盐的摩尔比为3～8∶1；所述的水溶性二价锰盐优选：氯化锰(MnCl2)、硫酸锰(MnSO4)或硝酸锰(Mn(NO3)2)；所述的无机碱优选：氢氧化钠、氢氧化锂或氢氧化钾；所述的阳离子型表面活性剂优选：十六烷基三甲基溴化铵、十二烷基三甲基氯化铵或十二烷基二甲基苄基氯化铵；所述的水溶性二价钴盐或三价铁盐优选：二价钴、三价铁的盐酸盐或硝酸盐。Wherein: the cationic surfactant consumption is 0.1～5wt%; The mol ratio of cationic surfactant and divalent manganese salt is 2～6: 1; The mol ratio of inorganic base and divalent manganese salt is 3～5wt%. 8:1; the preferred water-soluble divalent manganese salt: manganese chloride (MnCl 2 ), manganese sulfate (MnSO 4 ) or manganese nitrate (Mn(NO 3 ) 2 ); the preferred inorganic base: hydroxide Sodium, lithium hydroxide or potassium hydroxide; Described cationic surfactant is preferably: hexadecyltrimethylammonium bromide, dodecyltrimethylammonium chloride or dodecyldimethylbenzyl ammonium chloride; the water-soluble divalent cobalt salt or ferric salt is preferably: hydrochloride or nitrate of divalent cobalt and ferric iron.
本发明方法制得的二氧化锰为层状结构且层间距较大，是由于阳离子型表面活性剂起到模板作用，OH-或形成的[Mn(OH)6]4-组装到阳离子型表面活性剂周围形成配合物，为了保持配合物的电中性，Mn2+将不断进入配合物中最终形成介观结构的层状二氧化锰，阳离子型表面活性剂位于二氧化锰层间。The manganese dioxide prepared by the method of the present invention has a layered structure and the interlayer distance is relatively large, because the cationic surfactant acts as a template, and OH- or formed [Mn(OH) 6 ] 4- assembles to the cationic surface A complex is formed around the active agent. In order to maintain the electrical neutrality of the complex, Mn 2+ will continuously enter the complex to form a layered manganese dioxide with a mesoscopic structure. The cationic surfactant is located between the manganese dioxide layers.
层状二氧化锰的层间结构通常不稳定，易受热、层间离子脱出或嵌入的影响。本发明方法中，由于引入了Co2+或Fe3+，使得层状二氧化锰中的部分锰被Co2+或Fe3+所取代，Co2+或Fe3+起到骨架稳定剂的作用，使得二氧化锰的层间结构比较稳定。The interlayer structure of layered MnO2 is usually unstable and susceptible to heat, interlayer ion extraction or intercalation. In the method of the present invention, due to the introduction of Co 2+ or Fe 3+ , part of the manganese in the layered manganese dioxide is replaced by Co 2+ or Fe 3+ , and Co 2+ or Fe 3+ acts as a skeleton stabilizer. The effect makes the interlayer structure of manganese dioxide more stable.
本发明合成稳定结构的大层间距层状二氧化锰的工艺简便易行。The process of synthesizing the layered manganese dioxide with large interlayer distance and stable structure is simple and easy.
具体实施方式：Detailed ways:
下面通过实施例对本发明作进一步的说明，其目的是为更好理解本发明的内容。因此，本发明的保护范围并不受实施例的限制。Below by embodiment the present invention will be further described, and its purpose is for better understanding content of the present invention. Therefore, the protection scope of the present invention is not limited by the examples.
实施例1Example 1
先将十六烷基三甲基溴化铵10.0g(27.4mmol)放入盛有500ml去离子水的反应器中，待十六烷基三甲基溴化铵完全溶解后，加入含氢氧化锂1.64g(68.5mmol)300ml水溶液，混合均匀后，在电动搅拌下，逐渐加入含有氯化锰1.78g(13.7mmol)和氯化亚钴0.36g(2.74mmol)200ml水溶液，控制反应温度为30℃，搅拌反应3小时，然后升温至100℃，继续老化反应12小时，过滤、水洗，将得到的固体物置于75℃烘干，即得黑色的层状二氧化锰粉末2.78g，XRD测试表明其层间距为2.32nm。First put 10.0g (27.4mmol) of cetyltrimethylammonium bromide into a reactor filled with 500ml of deionized water. After the cetyltrimethylammonium bromide is completely dissolved, add the Lithium 1.64g (68.5mmol) 300ml aqueous solution, after mixing evenly, under electric agitation, add and contain manganese chloride 1.78g (13.7mmol) and cobaltous chloride 0.36g (2.74mmol) 200ml aqueous solution gradually, control reaction temperature to be 30 ℃, stirred and reacted for 3 hours, then raised the temperature to 100℃, continued the aging reaction for 12 hours, filtered, washed with water, and dried the obtained solid at 75℃ to obtain 2.78g of black layered manganese dioxide powder, XRD test showed Its layer spacing is 2.32nm.
实施例2Example 2
先将十六烷基三甲基溴化铵10.0g(27.4mmol)放入盛有500ml去离子水的反应器中，待十六烷基三甲基溴化铵完全溶解后，加入含氢氧化锂1.64g(68.5mmol)300ml水溶液，混合均匀后，在电动搅拌下，逐渐加入含有氯化锰1.21g(9.6mmol)和氯化亚钴0.62g(4.8mmol)200ml水溶液，控制反应温度为30℃，搅拌反应3小时，然后升温至100℃，继续老化反应12小时，过滤、水洗，将得到的固体物置于75℃烘干，即得黑色的层状二氧化锰粉末2.1g，XRD测试表明其层间距为2.06nm。First put 10.0g (27.4mmol) of cetyltrimethylammonium bromide into a reactor filled with 500ml of deionized water. After the cetyltrimethylammonium bromide is completely dissolved, add the Lithium 1.64g (68.5mmol) 300ml aqueous solution, after mixing evenly, under electric agitation, add and contain manganese chloride 1.21g (9.6mmol) and cobaltous chloride 0.62g (4.8mmol) 200ml aqueous solution gradually, control reaction temperature to be 30 ℃, stirred and reacted for 3 hours, then raised the temperature to 100℃, continued the aging reaction for 12 hours, filtered, washed with water, and dried the obtained solid at 75℃ to obtain 2.1g of black layered manganese dioxide powder, XRD test showed Its layer spacing is 2.06nm.
实施例3Example 3
先将十六烷基三甲基溴化铵40.0g(109.7mmol)放入盛有500ml去离子水的反应器中，待十六烷基三甲基溴化铵完全溶解后，加入含氢氧化锂6.56g(273.8mmol)300ml水溶液，混合均匀后，在电动搅拌下，逐渐加入含有氯化锰7.12g(54.8mmol)和氯化亚钴1.44g(11.0mmol)200ml水溶液，控制反应温度为70℃，搅拌反应3小时，然后升温至100℃，继续老化反应12小时，过滤、水洗，将得到的固体物置于75℃烘干，即得黑色的层状二氧化锰粉末8.22g，XRD测试表明其层间距为1.73nm。First put 40.0g (109.7mmol) of cetyltrimethylammonium bromide into a reactor filled with 500ml of deionized water. After the cetyltrimethylammonium bromide is completely dissolved, add the Lithium 6.56g (273.8mmol) 300ml aqueous solution, after mixing evenly, under electric stirring, add and contain manganese chloride 7.12g (54.8mmol) and cobaltous chloride 1.44g (11.0mmol) 200ml aqueous solution gradually, control reaction temperature to be 70 ℃, stirred and reacted for 3 hours, then raised the temperature to 100℃, continued the aging reaction for 12 hours, filtered, washed with water, and dried the obtained solid at 75℃ to obtain 8.22g of black layered manganese dioxide powder, XRD test showed Its layer spacing is 1.73nm.
实施例4Example 4
先将十六烷基三甲基溴化铵l0.0g(27.4mmol)放入盛有500ml去离子水的反应器中，待十六烷基三甲基溴化铵完全溶解后，加入含氢氧化钠2.74g(68.5mmol)300ml水溶液，混合均匀后，在电动搅拌下，逐渐加入含有硫酸锰2.07g(13.7mmol)和硝酸亚钴0.5g(2.74mmol)200ml水溶液，控制反应温度为30℃，搅拌反应3小时，然后升温至100℃，继续老化反应12小时，过滤、水洗，将得到的固体物置于75℃烘干，即得黑色的层状二氧化锰粉末2.96g，XRD测试表明其层间距为2.65nm。First put 10.0 g (27.4 mmol) of cetyltrimethylammonium bromide into a reactor filled with 500 ml of deionized water, and after the cetyltrimethylammonium bromide is completely dissolved, add hydrogen-containing Sodium oxide 2.74g (68.5mmol) 300ml aqueous solution, after mixing evenly, under electric stirring, gradually add manganese sulfate 2.07g (13.7mmol) and cobaltous nitrate 0.5g (2.74mmol) 200ml aqueous solution, control the reaction temperature to 30 ℃ , stirred and reacted for 3 hours, then raised the temperature to 100°C, continued the aging reaction for 12 hours, filtered, washed with water, and dried the obtained solid at 75°C to obtain 2.96g of black layered manganese dioxide powder. XRD test showed that The layer spacing is 2.65nm.
实施例5Example 5
先将十六烷基三甲基溴化铵l0.0g(27.4mmol)放入盛有500ml去离子水的反应器中，待十六烷基三甲基溴化铵完全溶解后，加入含氢氧化锂0.82g(34.3mmol)300ml水溶液，混合均匀后，在电动搅拌下，逐渐加入含有氯化锰0.89g(6.85mmol)和氯化亚钴0.18g(1.37mmol)200ml水溶液，控制反应温度为30℃，搅拌反应3小时，然后升温至100℃，继续老化反应12小时，过滤、水洗，将得到的固体物置于75℃烘干，即得黑色的层状二氧化锰粉末1.56g，XRD测试表明其层间距为2.82nm。First put 10.0 g (27.4 mmol) of cetyltrimethylammonium bromide into a reactor filled with 500 ml of deionized water, and after the cetyltrimethylammonium bromide is completely dissolved, add hydrogen-containing Lithium oxide 0.82g (34.3mmol) 300ml aqueous solution, after mixing evenly, under electric agitation, add gradually and contain manganese chloride 0.89g (6.85mmol) and cobaltous chloride 0.18g (1.37mmol) 200ml aqueous solution, control reaction temperature to be Stir and react at 30°C for 3 hours, then raise the temperature to 100°C, continue the aging reaction for 12 hours, filter, wash with water, and dry the obtained solid at 75°C to obtain 1.56g of black layered manganese dioxide powder, XRD test It shows that the interlayer spacing is 2.82nm.
实施例6Example 6
先将十六烷基三甲基溴化铵10.0g(27.4mmol)放入盛有500ml去离子水的反应器中，待十六烷基三甲基溴化铵完全溶解后，加入含氢氧化锂2.63g(109.6mmol)300ml水溶液，混合均匀后，在电动搅拌下，逐渐加入含有氯化锰1.78g(13.7mmol)和氯化亚钴0.36g(2.74mmol)200ml水溶液，控制反应温度为30℃，搅拌反应3小时，然后升温至100℃，继续老化反应12小时，过滤、水洗，将得到的固体物置于75℃烘干，即得黑色的层状二氧化锰粉末3.28g，XRD测试表明其层间距为3.05nm。First put 10.0g (27.4mmol) of cetyltrimethylammonium bromide into a reactor filled with 500ml of deionized water. After the cetyltrimethylammonium bromide is completely dissolved, add the Lithium 2.63g (109.6mmol) 300ml aqueous solution, after mixing evenly, under electric agitation, add and contain manganese chloride 1.78g (13.7mmol) and cobaltous chloride 0.36g (2.74mmol) 200ml aqueous solution gradually, control reaction temperature to be 30 ℃, stirred and reacted for 3 hours, then raised the temperature to 100℃, continued the aging reaction for 12 hours, filtered, washed with water, and dried the obtained solid at 75℃ to obtain 3.28g of black layered manganese dioxide powder, XRD test showed Its layer spacing is 3.05nm.
实施例7Example 7
先将十六烷基三甲基溴化铵10.0g(27.4mmol)放入盛有500ml去离子水的反应器中，待十六烷基三甲基溴化铵完全溶解后，加入含氢氧化锂1.64g(68.5mmol)300ml水溶液，混合均匀后，在电动搅拌下，逐渐加入含有氯化锰1.78g(13.7mmol)和氯化亚钴0.36g(2.74mmol)200ml水溶液，控制反应温度为20℃，搅拌反应3小时，然后升温至100℃，继续老化反应160小时，过滤、水洗，将得到的固体物置于75℃烘干，即得黑色的层状二氧化锰粉末2.92g，XRD测试表明其层间距为2.54nm。First put 10.0g (27.4mmol) of cetyltrimethylammonium bromide into a reactor filled with 500ml of deionized water. After the cetyltrimethylammonium bromide is completely dissolved, add the Lithium 1.64g (68.5mmol) 300ml aqueous solution, after mixing evenly, under electric agitation, add and contain manganese chloride 1.78g (13.7mmol) and cobaltous chloride 0.36g (2.74mmol) 200ml aqueous solution gradually, control reaction temperature to be 20 ℃, stirred and reacted for 3 hours, then raised the temperature to 100℃, continued the aging reaction for 160 hours, filtered, washed with water, and dried the obtained solid at 75℃ to obtain 2.92g of black layered manganese dioxide powder, XRD test showed Its layer spacing is 2.54nm.
实施例8Example 8
先将十二烷基三甲基氯化铵7.2g(27.4mmol)放入盛有500ml去离子水的反应器中，待十二烷基三甲基氯化铵完全溶解后，加入含氢氧化钾3.84g(68.5mmol)300ml水溶液，混合均匀后，在电动搅拌下，逐渐加入含有硝酸锰2.45g(13.7mmol)和硝酸铁0.66g(2.74mmol)200ml水溶液，控制反应温度为30℃，搅拌反应3小时，然后升温至100℃，继续老化反应12小时，过滤、水洗，将得到的固体物置于75℃烘干，即得黑色的层状二氧化锰粉末2.68g，XRD测试表明其层间距为2.36nm。First put 7.2g (27.4mmol) of dodecyltrimethylammonium chloride into a reactor filled with 500ml of deionized water. After the dodecyltrimethylammonium chloride is completely dissolved, add the Potassium 3.84g (68.5mmol) 300ml aqueous solution, after mixing evenly, under electric stirring, gradually add the 200ml aqueous solution containing manganese nitrate 2.45g (13.7mmol) and ferric nitrate 0.66g (2.74mmol), control the reaction temperature to be 30 ℃, stir React for 3 hours, then raise the temperature to 100°C, continue the aging reaction for 12 hours, filter, wash with water, and dry the obtained solid at 75°C to obtain 2.68g of black layered manganese dioxide powder. XRD test shows that the interlayer distance 2.36nm.
实施例9Example 9
先将十二烷基二甲基苄基氯化铵9.3g(27.4mmol)放入盛有500ml去离子水的反应器中，待十二烷基二甲基苄基氯化铵完全溶解后，加入含氢氧化钠2.74g(68.5mmol)300ml水溶液，混合均匀后，在电动搅拌下，逐渐加入含有硫酸锰2.07g(13.7mmol)和氯化铁0.45g(2.74mmol)200ml水溶液，控制反应温度为30℃，搅拌反应3小时，然后升温至100℃，继续老化反应12小时，过滤、水洗，将得到的固体物置于75℃烘干，即得黑色的层状二氧化锰粉末2.88g，XRD测试表明其层间距为2.48nm。First dodecyl dimethyl benzyl ammonium chloride 9.3g (27.4mmol) is put into the reactor that fills 500ml deionized water, after treating that dodecyl dimethyl benzyl ammonium chloride dissolves completely, Add 300ml aqueous solution containing 2.74g (68.5mmol) of sodium hydroxide, mix evenly, under electric stirring, gradually add 200ml aqueous solution containing 2.07g (13.7mmol) of manganese sulfate and 0.45g (2.74mmol) of ferric chloride, and control the reaction temperature Stir and react for 3 hours at 30°C, then raise the temperature to 100°C, continue the aging reaction for 12 hours, filter, wash with water, and dry the obtained solid at 75°C to obtain 2.88g of black layered manganese dioxide powder, XRD Tests show that its interlayer spacing is 2.48nm.
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