CN115321608B - 一种从冶金矿渣中回收金属制备电池正极材料的方法 - Google Patents
一种从冶金矿渣中回收金属制备电池正极材料的方法 Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 239000010406 cathode material Substances 0.000 title description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000011572 manganese Substances 0.000 claims abstract description 38
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 22
- 239000010941 cobalt Substances 0.000 claims abstract description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 22
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims abstract description 18
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 8
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
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- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000010405 anode material Substances 0.000 claims abstract 4
- 239000000243 solution Substances 0.000 claims description 10
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 abstract description 9
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 abstract description 4
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- 239000000203 mixture Substances 0.000 description 6
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910011669 LiNi0.7Co0.2Mn0.1O2 Inorganic materials 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
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- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid 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
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- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
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Classifications
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
- C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- H—ELECTRICITY
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- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
本发明属于工业固废资源化利用领域，尤其涉及一种从冶金矿渣中回收金属制备电池正极材料的方法。本发明提供一种从冶金矿渣中回收金属制备电池正极材料的方法，包括如下步骤：(1)采用酸浸的方法分别从含金属钴、镍、锰的冶金矿渣提取出钴溶液、镍溶液和锰溶液；(2)将三种金属提取液混合后与六亚甲基四胺进行水热反应，反应后收集固体得到NixCoyMn1‑x‑y(OH)2前驱体；(3)NixCoyMn1‑x‑y(OH)2前驱体进行混锂煅烧得到镍钴锰酸锂三元电池正极材料。本方法操作简单，能有效地从冶金矿渣中回收钴镍锰资源并再生为镍钴锰酸锂三元电极材料，可应用于工业冶金矿渣的资源化回收。
Description
技术领域
本发明属于工业固废资源化利用领域，尤其涉及一种从冶金矿渣中回收金属制备电池正极材料的方法。
背景技术
冶金矿渣是指金属冶炼过程中产生的以硅铝酸盐矿物为主要成分的冶金矿渣，堆存冶金矿渣的渣场需占用大量土地，并且在堆存过程中受各种气候条件的侵蚀，矿渣炉渣中含有的重金属和其他有毒元素会逐渐溶解进入环境，从而污染水体和土壤。现在工业上处理冶金矿渣的方法主要有两种，一种是用各种火法冶金方法，使矿渣中的金属转化为元素状态或其硫化物，但这方法存在二氧化硫污染问题且回收率不高；另一种是将炉渣硫酸化焙烧，将其中的重金属转化为硫酸盐，然后用热水或弱酸浸出，这方法同样存在二氧化硫污染问题，且需大型设备。冶金矿渣主要是水淬粒化高炉矿渣、水淬锰渣、水淬镍铁渣，废渣中常含有各种金属元素，如镍、钴、锰等。因此，如何将大量的冶金矿渣充分利用，提取其中的有用元素并加以应用(比如制备出锂离子电池正极材料)，是需要解决的技术难题。
锂离子电池由于其能量高、电压高、工作温度范围宽、使用寿命长等优点已经成为日常生活中必不可少的一种绿色电池。镍钴锰酸锂材料作为成本较低且性能与钴酸锂电学性能相近的一种电池正极材料，已经逐渐取代钴酸锂，成为最常用的锂离子电池正极材料之一。目前有一些研究通过将废旧锂离子电池进行拆解、粉碎后再采用化学方法将其中的金属元素浸出，二次制备镍钴锰酸锂材料。然而相比于废旧电池，冶金矿渣、电镀污泥中的可回收金属资源更多，因此，从冶金矿渣中回收镍钴锰资源作为原料代替常规原料，并再生镍钴锰酸锂材料，具有较高的环境和经济效益。
发明内容
为了克服上述现有技术的不足，本发明的目的是提供一种从冶金矿渣中回收金属制备电池正极材料的方法，该方法可以将冶金矿渣作为原料制备镍钴锰酸锂材料，降低生产成本且有效处理矿渣。
为实现上述目的，本发明是通过以下技术方案来实现的：
本发明提供一种从冶金矿渣中回收金属制备电池正极材料的方法，其特征在于，包括以下步骤：
S1、采用酸浸的方法分别从含镍冶金矿渣、含钴冶金矿渣和含锰冶金矿渣提取出镍提取液、钴提取液和锰提取液；
S2、将镍提取液、钴提取液和锰提取液混合，再将混合溶液与六亚甲基四胺进行水热反应，反应后收集固体得到NixCoyMn1-x-y(OH)2前驱体；
S3、将NixCoyMn1-x-y(OH)2前驱体与锂源混合后煅烧得到镍钴锰酸锂三元电池正极材料。
优选地，步骤1中，所述酸浸为采用1～2mol/L的酸溶液进行。
优选地，步骤2中，所述混合溶液中镍、钴、锰的摩尔比为x:y:(1-x-y)，与所述NixCoyMn1-x-y(OH)2前驱体的比例一致，其中0＜x＜1，0＜y＜1，0＜x+y＜1。
优选地，步骤2中，所述六亚甲基四胺的摩尔用量与镍、钴、锰的总摩尔之比为(1～3):1。
优选地，步骤2中，所述水热反应为在150～200℃下水热反应10～24h。
优选地，步骤3中，所述锂源为碳酸锂、氯化锂、硝酸锂、氢氧化锂中的任一种或多种，所述锂源与NixCoyMn1-x-y(OH)2前驱体的摩尔比为(1.1～1.2):1。
优选地，步骤3中，所述煅烧为先以1～3℃/min的升温速率升温至450～500℃反应6～7h；再以1～3℃/min的升温速率升温至750～800℃反应15～17h。
与现有技术相比，本发明的有益效果是：
本发明提供了一种从冶金矿渣中回收金属制备电池正极材料的方法，先采用酸浸的方法分别从含金属钴、镍、锰的冶金矿渣提取出钴溶液、镍溶液和锰溶液；再将三种金属提取液混合后与六亚甲基四胺进行水热反应得到金属前驱体；最后对金属前驱体进行混锂煅烧后得到镍钴锰酸锂三元电池正极材料。本方法可行可靠、操作简单、效率高，能有效地从冶金矿渣中回收镍钴锰资源并再生为镍钴锰酸锂材料，将冶金矿渣作为原料代替部分常规原料，降低生产成本且有效处理了矿渣。本方法制备得到的镍钴锰酸锂电池正极材料具有170mA/mg的大起始容量、75％的高起始库伦效率和优良的电池性能循环稳定性。
附图说明
图1为从冶金矿渣中回收金属制备电池正极材料的方法制备流程图；
图2为实施例1的镍钴锰酸锂电池正极材料的X射线衍射图。
具体实施方式
下面对本发明的具体实施方式作进一步说明。在此需要说明的是，对于这些实施方式的说明用于帮助理解本发明，但并不构成对本发明的限定。此外，下面所描述的本发明各个实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互组合。
下述实施例中的实验方法，如无特殊说明，均为常规方法，下述实施例中所用的试验材料，如无特殊说明，均为可通过常规的商业途径购买得到的。
实施例1LiNi0.333Co0.333Mn0.333O2电极材料的制备
本实施例中，所用含镍冶金矿渣为镀镍生产过程中的含镍废水经物化处理后产生的污泥，主要金属含量为91％Ni、4％Fe、1.4％Na；所用含钴冶金矿渣为含钴转炉渣，主要金属元素含量为32％Fe、7％Ni、7％Co、1％Cu；所有含锰冶金矿渣为加工后的锰矿渣，主要金属含量为9％Fe、9％Ca、8％Mn、5％Al、1.5％Mg。制备方法如图1所示，具体步骤如下：
(1)分别取经干燥和粉碎后的含镍冶金矿渣，含钴冶金矿渣和含锰冶金矿渣各10g分别浸泡在100ml 1mol/L的H2SO4溶液中，在25℃下搅拌3h后过滤得到含金属离子的上清液，即镍提取液、钴提取液和锰提取液，测得镍提取液浓度为0.32mol/L、钴提取液浓度为0.1mol/L、锰提取液浓度为0.1mol/L。
(2)将镍提取液、钴提取液和锰提取液混合，制成Ni、Co、Mn的摩尔比为1:1:1的30ml混合溶液，然后将六亚甲基四胺加入到混合溶液中，六亚甲基四胺的摩尔用量与镍、钴、锰的总摩尔量之比为2:1，搅拌至溶解后置于反应釜中，在200℃下进行水热反应12h；
(3)将反应后的混合溶液进行离心收集固体，用水和无水乙醇分别洗涤三次后放入烘箱干燥，得到Ni0.333Co0.333Mn0.333(OH)2前驱体；
(4)将Ni0.333Co0.333Mn0.333(OH)2前驱体与碳酸锂混合，碳酸锂与金属前驱体物质的量之比为1.05:1，混合后进行煅烧，先以2℃/min的升温速率升温至450℃反应6h，再以2℃/min的升温速率升温至750℃反应15h，制备得到LiNi0.333Co0.333Mn0.333O2电池正极材料。
实施例2LiNi0.8Co0.1Mn0.1O2电极材料的制备
制备方法同实施例1，不同之处在于：步骤2混合溶液中Ni、Co、Mn的摩尔比为8:1:1，制备得到LiNi0.8Co0.1Mn0.1O2电极材料。
实施例3LiNi0.7Co0.2Mn0.1O2电极材料的制备
制备方法同实施例1，不同之处在于：步骤2混合溶液中Ni、Co、Mn的摩尔比为7:2:1，制备得到LiNi0.7Co0.2Mn0.1O2电极材料。
实施例1镍钴锰酸锂电池正极材料的性能表征
(1)镍钴锰酸锂电池正极材料的X射线衍射谱表征
采用X射线衍射仪对实施例1制备的镍钴锰酸锂电极材料进行X射线衍射xrd分析，分析谱如图2所示，显示样品的主要物相为镍钴锰酸锂(LiNi0.333Co0.333Mn0.333O2)，且结晶性良好，无杂相；对实施2和3也进行xrd分析，显示样品物相同样为为镍钴锰酸锂，证明本发明成功利用冶金矿渣渣制备镍钴锰酸锂电极材料。
(2)镍钴锰酸锂电极材料的电化学性能表征
对实施例1得到的正极材料进行正极片的制作和电池组装，组装步骤如下：将制备的镍钴锰酸锂材料按照正极材料：导电剂：粘结剂＝8:1:1的比例在研钵中研磨混合，将得到的浆料在铝箔上涂布、烘干、切片。以金属锂为负极，以聚丙烯微孔膜为隔膜，以碳酸乙烯酯：碳酸二甲酯＝1:1的混合液为电解液，组装为扣式电池。测得其性能为：初始容量为170mA/mg,起始库伦效率为75％，平均库伦效率为99％，循环100圈后容量保持90.8％，200圈后容量保持80％，表明采用废渣材料制成的电池的具有大起始容量、高起始库伦效率和优良的电池性能循环稳定性。
以上对本发明的实施方式作了详细说明，但本发明不限于所描述的实施方式。对于本领域的技术人员而言，在不脱离本发明原理和精神的情况下，对这些实施方式进行多种变化、修改、替换和变型，仍落入本发明的保护范围内。
Claims (1)
1.一种从冶金矿渣中回收金属制备电池正极材料的方法，其特征在于，包括以下步骤：
S1、采用酸浸的方法分别从含镍冶金矿渣、含钴冶金矿渣和含锰冶金矿渣提取出镍提取液、钴提取液和锰提取液；
S2、将镍提取液、钴提取液和锰提取液混合，再将混合溶液与六亚甲基四胺进行水热反应，反应后收集固体得到NixCoyMn1-x-y(OH)2前驱体；
S3、将NixCoyMn1-x-y(OH)2前驱体与锂源混合后煅烧得到镍钴锰酸锂三元电池正极材料；
步骤1中，所述酸浸为采用1mol/L的酸溶液进行；
步骤2中，所述六亚甲基四胺的摩尔用量与镍、钴、锰的总摩尔之比为2:1；
步骤2中，所述水热反应为在200℃下水热反应12h；
步骤3中，所述锂源为碳酸锂、氯化锂、硝酸锂、氢氧化锂中的任一种或多种，所述锂源与NixCoyMn1-x-y(OH)2前驱体的摩尔比为1.05:1；
步骤3中，所述煅烧为先以2℃/min的升温速率升温至450℃反应6h；再以2℃/min的升温速率升温至750℃反应15h；
步骤2中，x＝0.333，y＝0.333。
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