CN112791691A - 一种包覆型锂离子筛及其制备方法 - Google Patents
一种包覆型锂离子筛及其制备方法 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000011572 manganese Substances 0.000 claims abstract description 60
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 22
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000003463 adsorbent Substances 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 229910002993 LiMnO2 Inorganic materials 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 230000020477 pH reduction Effects 0.000 claims abstract description 9
- 229910014689 LiMnO Inorganic materials 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 150000002696 manganese Chemical class 0.000 claims abstract description 5
- 239000011247 coating layer Substances 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000011656 manganese carbonate Substances 0.000 claims description 5
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 229910002983 Li2MnO3 Inorganic materials 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical group [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical group [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 13
- 238000001179 sorption measurement Methods 0.000 description 19
- 229910052748 manganese Inorganic materials 0.000 description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910052596 spinel Inorganic materials 0.000 description 6
- 239000011029 spinel Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000012697 Mn precursor Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013068 LiMxMn2-xO4 Inorganic materials 0.000 description 1
- 229910013064 LiMxMn2−xO4 Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 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
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种制备包覆型锂离子筛的方法,包括如下步骤:S01:将锰盐在空气气氛下煅烧2‑10h得到Mn2O3;S02:将Mn2O3和锂盐混合研磨,100‑200℃高压反应釜中反应36‑72h,得到产物LiMnO2;其中,Mn2O3和锂盐中Li/Mn的摩尔配比为1~10:1;S03:在金属包覆试剂中加入0.5‑5g LiMnO2超声2‑10h,干燥6‑24h,后置于400‑600℃温度下煅烧2‑10h,得到氧化物包覆的Li1.6Mn1.6O4锂离子吸附剂;其中,所述金属包覆试剂与LiMnO2摩尔比为0.01‑0.08:1;S04:将所述氧化物包覆的Li1.6Mn1.6O4锂离子吸附剂进行酸化处理,酸化处理产物经洗涤干燥后即得到包覆型锂离子筛。本发明的包覆型锂离子筛晶胞结构更加稳定,解决了传统HMn2O4锂离子筛易溶损的难题,可多次重复循环使用。
Description
技术领域
本发明涉及锂离子筛领域,具体涉及一种包覆型锂离子筛及其制备方法。
背景技术
动力和储能锂电池在新能源的广泛应用促发了全球对锂资源的需求持续增加,它广泛应用于润滑剂、陶瓷、制药、电池、原子能等新兴领域,已成为国民经济和国防建设的重要战略资源。
目前尖晶石型锂锰氧化物(LMO)因具有高吸附量和Li+选择性引起了相当大的研究热点,包括LiMn2O4,Li1.33Mnl.67O4和Li1.6Mn1.6O4。在所有LMO尖晶石材料中,Li1.6Mn1.6O4最具有代表性,因其较高的理论吸附容量和经过几个循环后良好的稳定性。然而,锰的溶解不仅降低了吸附能力,而且在实际应用中污染了解吸液。限制了其工业化应用。掺杂改性被认为是改善尖晶石型吸附剂锰溶损的最简单有效的方法。引入掺杂离子的主要目的是提高锂锰氧化物尖晶石中锰的平均化学价,同时降低Mn3+的含量,抑制Jahn-Teller效应的发生或者增强八面体的化学键。Chitrakar等研究了LimMgxMn(III)yMn(IV)zO4(0≤x≥0.5)对酸处理过程中锰溶解的影响,结果表明,随着Mg/Mn比的增加,锂的吸附能力提高且吸附剂化学稳定性也随之提高。Xue等首次合成了掺杂Fe3O4的锂锰氧化物(LiMn2O4/Fe3O4)作为磁性离子筛前驱体,将Fe3O4掺杂到LMO中,使前驱体中Mn的平均价态从+3.48提高到+3.53,有利于提高其结构稳定性。Ma等制备了一系列LiMxMn2-xO4(M=Ni,Al,Ti;0≤x≥1)尖晶石型吸附剂并比较其在水溶液中的锂离子回收性能。结果表明,LiAl0.5Mn1.5O4在酸处理过程中表现出较高的Li+吸附率和较低的Mn和Al的溶损率,而LiNi0.5Mn1.5O4和LiTi0.5Mn1.5O4尖晶石的Li+吸附性能相对较差。Qian等通过用不同的过渡金属离子(Fe3+,Co2+)掺杂Li1.6Mn1.6O4来改善酸洗过程中的锰溶损率。吸附结果表明,与未掺杂的吸附剂(32.3mg/g)相比掺杂Fe3+和Co2+后的吸附量分别为35.3mg/g和35.4mg/g,且锰损率从5.43%降低为3.95%和4.42%。离子掺杂过程中要避免掺杂金属离子占据8a位置,阻碍锂离子的移动。
发明内容
本发明的目的是提供一种包覆型锂离子筛及其制备方法,具有吸附容量高、锰溶损少、循环稳定性高的优势。
为了实现上述目的,本发明采用如下技术方案:一种包覆型锂离子筛,包括内壳和包覆层,所述包覆层均匀覆盖在所述内壳外侧,所述内壳为Li1.6Mn1.6O4,所述包覆层为Li2O、Li2MnO3、MnO2中的任一种。
进一步的,所述包覆型锂离子筛的直径为45-55nm;所述包覆层厚度为2-4nm。
一种制备上述的包覆型锂离子筛的方法,包括如下步骤:
S01:将锰盐在空气气氛下煅烧2-10h得到Mn2O3;
S02:将Mn2O3和锂盐混合研磨,100-200℃高压反应釜中反应36-72h,得到产物LiMnO2;其中,Mn2O3和锂盐中Li/Mn的摩尔配比为1~10:1;
S03:在金属包覆试剂中加入LiMnO2超声2-10h,干燥6-24h,后置于400-600℃温度下煅烧2-10h,得到氧化物包覆的Li1.6Mn1.6O4锂离子吸附剂;其中,所述金属包覆试剂与LiMnO2摩尔比为0.01-0.08:1;
S04:将所述氧化物包覆的Li1.6Mn1.6O4锂离子吸附剂进行酸化处理,酸化处理产物经洗涤干燥后即得到包覆型锂离子筛。
进一步的,所述锰盐为碳酸锰;所述金属包覆试剂为硝酸锰或硝酸锂。
进一步的,所述锂盐为为氢氧化锂或碳酸锂。
进一步的,所述酸化处理为采用盐酸或硫酸浸泡处理,所述盐酸或硫酸的浓度为0.25-0.5mol/L,浸泡时间为12-48h。
进一步的,所述步骤S02中超声后溶液置于马弗炉中于400-600℃温度下煅烧,且煅烧时控制升温速率为5-10℃/min。
进一步的,所述步骤S02中高压反应釜中反应温度为110-150℃。
进一步的,所述步骤S02中煅烧温度为350-450℃。
本发明具有如下有益效果:1、本发明的包覆型锂离子筛晶胞结构更加稳定,解决了传统HMn2O4锂离子筛易溶损的难题,可多次重复循环使用。
2、本发明的包覆型锂离子筛形貌优异,颗粒平均粒径小,比表面积较大,作为锂离子吸附剂时,其特定形貌有利于含锂液的充分接触,便于锂离子的嵌入与脱出,并且有利于保持材料的循环稳定性能。
3、本发明的制备方法简单、条件温合、产品一致性好、稳定性好、易于实现工业化。
附图说明
图1为本发明实施例1制备的包覆型锂离子筛的XRD图;
图2为本发明实施例1制备的包覆型锂离子筛的SEM图;
图3为本发明实施例1制备的包覆型锂离子筛的TEM图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面结合附图对本发明的具体实施方式做进一步的详细说明。
本发明公开了一种包覆型锂离子筛,包括内壳和包覆层,包覆层均匀覆盖在内壳外侧,内壳为Li1.6Mn1.6O4,包覆层为Li2O、Li2MnO3、MnO2中的任一种。其中,包覆型锂离子筛的直径为45-55nm;包覆层厚度为2-4nm。
优选地,本发明中包覆型锂离子筛的晶型为尖晶石晶型,锂离子筛为多面体颗粒,且其平均颗粒直径为50nm左右,包覆层约3nm左右,结晶性较好。本发明的包覆型锂离子筛的锰溶损率明显降低,通过多次吸附循环后仍然保持尖晶石结构,说明此吸附剂具有更加稳定的晶体结构。有利于解决锰系吸附剂在实际应用中的锰溶损及稳定性等难题。另外,本发明的包覆型锂离子筛颗粒平均粒径小,锂离子筛不直接与溶液接触,有利于保持材料的循环稳定性能。
实施例1
一种制备包覆型锂离子筛的方法,包括如下步骤:
S01:将MnCO3在空气气氛下煅烧5h得到Mn2O3;
S02:将Mn2O3和锂盐混合研磨,转移至100mL聚四氟乙烯内衬的不锈钢反应釜中,将反应釜放入烘箱中,在120℃的反应温度下进行水热反应,反应时间为48h;待反应结束后,将得到的产物放入烘箱中于60℃下干燥12h,得到产物LiMnO2;其中,Mn2O3和锂盐中Li/Mn的摩尔配比为1:1;
值得说明的是,锂盐的实际使用量为其为其理论用量的1.00-1.05倍,这是因为由于一次煅烧即可得到所需前驱体产品,锂盐损失较小,故锂盐的用量可采用理论量或稍过量,锂盐用量过多时,残留锂盐会影响产品性能。本发明中设置Mn2O3和锂盐中Li/Mn的摩尔配比时已经充分考虑到锂盐的理论用量和实际用量。
S03:在4M硝酸锂溶液中加入1g LiMnO2超声4h,60℃下干燥20h,干燥后的粉末在研磨中充分混合后,放入坩埚并置于马弗炉中,于空气中在5℃/min的升温速率下升温到450℃,高温固相反应4h,得到氧化物包覆的Li1.6Mn1.6O4锂离子吸附剂;其中,金属包覆试剂与LiMnO2摩尔比为0.04:1,若包覆量太低,达不到改性的目的;包覆量过高,阻碍锂离子脱嵌,使得锂离子筛的吸附容量下降。
本发明包覆元素选用锂、锰是考虑到其二者在反应过程中形成对酸性环境稳定的Li2MnO3,便于提高锂离子筛整体稳定性,使得煅烧后材料的晶型结构更稳定,在后续锂离子筛的吸附与解吸过程中不易溶损,提高材料的使用寿命。
金属包覆试剂的阴离子优选硝酸根,因为硝酸根加热条件下容易形成相应的氧化物和二氧化氮气体,不带入其他杂志元素。
S04:将氧化物包覆的Li1.6Mn1.6O4锂离子吸附剂放入20mL浓度为0.5mol/L的稀盐酸中,常温下震荡24h后完成脱锂,将得到的产物进行过滤、洗涤后放入烘箱中于60℃下干燥12h,得到的粉体材料即为本实施例中包覆型锂离子筛。其中,酸化浸泡时间过短则锂离子浸出不充分,浸出时间过长则会过度酸化,使得Mn溶损。
附图1为实施例1制备的包覆型锂离子筛的XRD图,结合XRD图谱可以看出表面包覆没有改变前驱体的物相组成,均得到了晶型良好、纯相Li1.6Mn1.6O4。当包覆MnO2时,XRD图显示为单一Li1.6Mn1.6O4的特征衍射峰;当包覆Li2O、Li2MnO3时,出现了Li2MnO3的特征峰。
图2为实施例1制备的包覆型锂离子筛的SEM图;图3为实施例1制备的包覆型锂离子筛的TEM图,SEM图显示颗粒尺寸在100nm左右。多面体小颗粒团聚成球形二次颗粒,由图可以看出未包覆的前驱体颗粒较大,颗粒表面比较光滑,而包覆金属氧化物的前驱体颗粒凹凸不平颗粒变小。为了检测金属氧化物在前驱体Li1.6Mn1.6O4表面上的包覆厚度,用高分辨透射电镜HRTEM对包覆的前驱体表面进行分析,从图中看出,在基体Li1.6Mn1.6O4表面上有一层粗糙的包覆层,厚度约3nm左右,再次证明Li1.6Mn1.6O4成功包覆了金属氧化物层。
实施例2
一种制备包覆型锂离子筛的方法,包括如下步骤:
S01:将MnCO3在空气气氛下煅烧2h得到Mn2O3;
S02:将Mn2O3和锂盐混合研磨,转移至100mL聚四氟乙烯内衬的不锈钢反应釜中,将反应釜放入烘箱中,在120℃的反应温度下进行水热反应,反应时间为36h;待反应结束后,将得到的产物放入烘箱中于60℃下干燥12h,得到产物LiMnO2;其中,Mn2O3和锂盐中Li/Mn的摩尔配比为10:1;
S03:在4M硝酸锂溶液中加入1g LiMnO2超声2h,60℃下干燥36h,干燥后的粉末在研磨中充分混合后,放入坩埚并置于马弗炉中,于空气中在7℃/min的升温速率下升温到400℃,高温固相反应2h,得到氧化物包覆的Li1.6Mn1.6O4锂离子吸附剂;其中,金属包覆试剂与LiMnO2摩尔比为0.01:1。
S04:将氧化物包覆的Li1.6Mn1.6O4锂离子吸附剂放入浓度为0.4mol/L的稀盐酸中,常温下震荡24h后完成脱锂,将得到的产物进行过滤、洗涤后放入烘箱中于60℃下干燥12h,得到的粉体材料即为本实施例中包覆型锂离子筛。
实施例3
一种制备包覆型锂离子筛的方法,包括如下步骤:
S01:将MnCO3在空气气氛下煅烧10h得到Mn2O3;
S02:将Mn2O3和锂盐混合研磨,转移至100mL聚四氟乙烯内衬的不锈钢反应釜中,将反应釜放入烘箱中,在200℃的反应温度下进行水热反应,反应时间为72h;待反应结束后,将得到的产物放入烘箱中于60℃下干燥12h,得到产物LiMnO2;其中,Mn2O3和锂盐中Li/Mn的摩尔配比为5:1;
S03:在4M硝酸锰溶液中加入1g LiMnO2超声10h,60℃下干燥36h,干燥后的粉末在研磨中充分混合后,放入坩埚并置于马弗炉中,于空气中在10℃/min的升温速率下升温到600℃,高温固相反应10h,得到氧化物包覆的Li1.6Mn1.6O4锂离子吸附剂;其中,金属包覆试剂与LiMnO2摩尔比为0.08:1。
S04:将氧化物包覆的Li1.6Mn1.6O4锂离子吸附剂放入浓度为0.4mol/L的稀硫酸中,常温下震荡24h后完成脱锂,将得到的产物进行过滤、洗涤后放入烘箱中于60℃下干燥12h,得到的粉体材料即为本实施例中包覆型锂离子筛。
对比例1
对比例1与实施例1的区别仅在于步骤S02中在去离子水中加入1g LiMnO2超声4h。
实验例1
初始锂离子浓度为165mg/L的卤水20mL,溶液pH为12.0,分别加入实施例1-3以及对比例1中的包覆型锂离子筛0.1g,在25℃、反应时间24h的条件下,测得其吸附容量如表1中首次吸附容量所示;吸附锂离子之后的锂离子筛经无机酸酸洗后离子筛可以重复使用,本实验例对酸洗之后的锂离子筛继续进行第五次吸附容量和第十次吸附容量测试,测试方法与首次吸附容量的测试方法相同。
表1不同实施例及对比例锂离子筛的吸附容量
可以看出:(1)相比于对比例1中单纯的锂离子筛,本发明制备的包覆型锂离子筛对于锂离子的吸附容量大幅度增加;说明本申请制备的包覆型锂离子筛吸附容量高,对锂离子的选择性高。
(2)采用本发明方法制备的包覆型锂离子筛在使用过后进行酸洗,酸洗之后的包覆型锂离子筛对于锂离子的吸附容量在循环9次后,吸附能力保持在45%以上,说明其性能稳定,可以长期循环使用。
实施例2
采用如下方法测试实施例1-3以及对比例中锂离子筛的锰溶解损失:称取0.1g实施例1-3以及对比例1中的Mg掺杂改性的锂离子筛放入20ml含Li+165mg/L的盐湖卤水中,25℃下吸附48h后,将锂离子筛进行酸洗,在酸洗过程后取上清液使用原子吸收光谱仪或者ICP测试残留Mn2+的浓度;测试结果如表2所示。
表2不同实施例及对比例锂离子筛的锰溶解损失量
锰溶解损失量(%) | |
实施例1 | 1.3 |
实施例2 | 1.45 |
实施例3 | 1.8 |
对比例1 | 2.5 |
可以看出,本发明制备的Mg掺杂改性的锂离子筛的锰溶解损失量明显低于对比例1中单纯的锂离子筛的锰溶解损失量。
本发明的包覆型锂离子筛晶胞结构更加稳定,解决了传统HMn2O4锂离子筛易溶损的难题,可多次重复循环使用;本发明的包覆型锂离子筛形貌优异,颗粒平均粒径小,比表面积较大,作为锂离子吸附剂时,其特定形貌有利于含锂液的充分接触,便于锂离子的嵌入与脱出,并且有利于保持材料的循环稳定性能;本发明的制备方法简单、条件温合、产品一致性好、稳定性好、易于实现工业化。
以上所述仅为本发明的优选实施例,所述实施例并非用于限制本发明的专利保护范围,因此凡是运用本发明的说明书及附图内容所作的等同结构变化,同理均应包含在本发明所附权利要求的保护范围内。
Claims (9)
1.一种包覆型锂离子筛,其特征在于,包括内壳和包覆层,所述包覆层均匀覆盖在所述内壳外侧,所述内壳为Li1.6Mn1.6O4,所述包覆层为Li2O、Li2MnO3、MnO2中的任一种。
2.根据权利要求1所述的一种包覆型锂离子筛,其特征在于,所述包覆型锂离子筛的直径为45-55nm;所述包覆层厚度为2-4nm。
3.一种制备权利要求1所述的包覆型锂离子筛的方法,其特征在于,包括如下步骤:
S01:将锰盐在空气气氛下煅烧2-10h得到Mn2O3;
S02:将Mn2O3和锂盐混合研磨,100-200℃高压反应釜中反应36-72h,得到产物LiMnO2;其中,Mn2O3和锂盐中Li/Mn的摩尔配比为1~10:1;
S03:在金属包覆试剂中加入LiMnO2超声2-10h,干燥6-24h,后置于400-600℃温度下煅烧2-10h,得到氧化物包覆的Li1.6Mn1.6O4锂离子吸附剂;其中,所述金属包覆试剂与LiMnO2摩尔比为0.01-0.08:1;
S04:将所述氧化物包覆的Li1.6Mn1.6O4锂离子吸附剂进行酸化处理,酸化处理产物经洗涤干燥后即得到包覆型锂离子筛。
4.根据权利要求3所述的一种制备方法,其特征在于,所述锰盐为碳酸锰;所述金属包覆试剂为硝酸锰或硝酸锂。
5.根据权利要求3所述的一种制备方法,其特征在于,所述锂盐为为氢氧化锂或碳酸锂。
6.根据权利要求3所述的一种制备方法,其特征在于,所述酸化处理为采用盐酸或硫酸浸泡处理,所述盐酸或硫酸的浓度为0.25-0.5mol/L,浸泡时间为12-48h。
7.根据权利要求3所述的一种制备方法,其特征在于,所述步骤S02中超声后溶液置于马弗炉中于400-600℃温度下煅烧,且煅烧时控制升温速率为5-10℃/min。
8.根据权利要求3所述的一种制备方法,其特征在于,所述步骤S02中高压反应釜中反应温度为110-150℃。
9.根据权利要求3所述的一种制备方法,其特征在于,所述步骤S02中煅烧温度为350-450℃。
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CN116371387A (zh) * | 2023-02-28 | 2023-07-04 | 华东理工大学 | 一种阳离子掺杂改性的锂离子筛的制备方法 |
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