CN115448384B - 一种多层包覆钠离子正极材料用前驱体及其制备方法 - Google Patents
一种多层包覆钠离子正极材料用前驱体及其制备方法 Download PDFInfo
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- CN115448384B CN115448384B CN202211325451.3A CN202211325451A CN115448384B CN 115448384 B CN115448384 B CN 115448384B CN 202211325451 A CN202211325451 A CN 202211325451A CN 115448384 B CN115448384 B CN 115448384B
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- 239000002243 precursor Substances 0.000 title claims abstract description 46
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 28
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000010406 cathode material Substances 0.000 title description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000010949 copper Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000007774 positive electrode material Substances 0.000 claims abstract 4
- 239000000243 solution Substances 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 239000008139 complexing agent Substances 0.000 claims description 16
- 239000011572 manganese Substances 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910004028 SiCU Inorganic materials 0.000 claims description 4
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000012066 reaction slurry Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 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 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000012716 precipitator Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 12
- 239000013078 crystal Substances 0.000 abstract description 8
- 238000000151 deposition Methods 0.000 abstract description 4
- 239000011247 coating layer Substances 0.000 abstract description 3
- IREHHCMIJCTSKK-UHFFFAOYSA-H [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] IREHHCMIJCTSKK-UHFFFAOYSA-H 0.000 abstract description 2
- 230000032683 aging Effects 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 239000012691 Cu precursor Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NSVHEPGUBVSHMK-UHFFFAOYSA-N [Cu].[Si](O)(O)(O)O Chemical compound [Cu].[Si](O)(O)(O)O NSVHEPGUBVSHMK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/187—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates
- C01B33/193—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by acidic treatment of silicates of aqueous solutions of silicates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
- C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
本发明公开了一种多层包覆钠离子正极材料用前驱体及其制备方法，其前驱体主要是以镍锰或镍铁锰氢氧化物为基体，采用共沉积方法进行外层Cu包覆，共沉积Cu包覆反应结束后，通过陈化反应加入Si盐，水解进行二次Si包覆，最后通过预烧使得Cu(OH)2形成CuO;两次包覆过程中均不采用络合剂进行包覆；包覆铜的目的是提高钠离子电池的倍率性能，包覆硅此目的是防止首周充电过程中晶体结构进行崩塌形成无定形相进一步增加晶体结构的稳定性。本发明植被的前驱体的包覆层呈疏松形貌，有利于钠离子形成钠离子进出的快速通道。使制备的钠离子电池低温性能优良、容量较高、高倍率充放电、提高安全性能。
Description
技术领域
本发明属于钠离子电池材料技术领域，具体而言，涉及一种多层包覆钠离子正极材料用前驱体及其制备方法。
技术背景
近年来，新能源汽车受到越来越多的关注。作为核心部件，动力电池是新能源汽车发展关键之一。随着锂离子电池价格上涨、资源储量有限等问题的显现，资源分布广泛的钠离子电池逐渐进入人们的视野。
目前对于钠离子电池来说，由于钠离子半径比锂离子大，导致了钠离子嵌入、脱出传输过程相对缓慢，大幅降低了比容量和倍率性能。另外钠离子的嵌入也会引起基体材料的晶体结构变化，造成结构不稳定使其安全性能降低。
因此为了改善钠离子嵌入、脱出导致的容量与倍率性能降低以及晶体结构不稳定使其安全性能差，制备出性能更好的钠离子电池正极材料对于本领域有重要的意义。
发明内容
针对现有技术存在的问题，本发明的目的是提供一种多层包覆钠离子电池正极材料用前驱体及其制备方法。本发明制备的前驱体的包覆层呈疏松形貌，有利于钠离子形成钠离子进出的快速通道。使制备的钠离子电池低温性能优良、容量较高、高倍率充放电、提高安全性能。
本发明提供一种多层包覆钠离子正极材料用前驱体，所述前驱体表面疏松，外层Cu包覆均匀，所述前驱体其分子式为SiCu1-X-Y-zNixFeyMnZ(OH)2，其中,0.1≤X＜0.5，0≤Y≤0.9，0＜Z≤0.8;Si占比为0.05-1.0%。
本发明还提供了一种多层包覆钠离子正极材料用前驱体的制备方法，包括以下步骤：
（1）配制镍锰或镍铁锰的混合盐溶液A，配制铜盐溶液B,配制硅酸盐溶液C，配制沉淀剂溶液、络合剂溶液以及酸溶液；
（2）在反应釜中用纯水、络合剂溶液、沉淀剂溶液中的一种或多种配制成反应底液，并按照体积比1：5通入空气与氮气的混合气体，且流量为5L/min;
（3）然后，在反应底液中并流通入混合盐溶液A、沉淀剂溶液和络合剂溶液进行共沉淀反应,待粒经D50长至3.0-12.0um,停止反应；整个反应过程中控制反应体系的温度为35-80℃，pH值为10-13，络合剂含量为0.1~10g/L，搅拌速度为200～1000 rpm；
（4）将步骤（3）最终得到的反应浆料进行固液分离，分离得到的固相经洗涤脱水后得到含水量为5%-15%的前驱体材料。
（5）将步骤（4）最终得到的前驱体材料与纯水按照重量比1：1-3投入反应釜内，将步骤（1）中所配制好的铜盐溶液B与沉淀剂溶液并流进入反应釜中，维持反应的pH为8-12.5，沉淀剂溶液浓度为1-8mol/L，反应温度为35-70℃，搅拌速度400-800 rpm，反应3-15h停止反应 ，得到外层包覆铜的氢氧化物的前驱体；
（6）步骤（5）中的反应结束后，将步骤（1）中配制的硅酸盐溶液C与酸溶液并流进入步骤（5）的反应釜中，保持反应pH为7-10，搅拌速度100-500 rpm，反应0.5-5h停止反应，进行固液分离，分离后经过水洗、烘干得到包覆铜硅的氢氧化物前驱体；
（7）将步骤（6）得到的包覆铜硅的氢氧化物前驱体，在150-250℃下进行预烧得到外层包覆氧化铜的SiCu1-X-Y-MNixFeyMnZ(OH)2前驱体。
进一步，所述镍锰或镍铁锰的混合盐溶液A浓度为1.0-2.5mol/L, 所述铜盐溶液B的浓度为0.5-2.0mol/L，所述硅酸盐溶液C的浓度为100-500g/L ；
进一步，所述镍锰或镍铁锰的混合盐溶液为硫酸盐、氯化盐、硝酸盐中的一种或多种，所述铜盐为硫酸铜、氯化铜中的至少一种；所述硅酸盐为硅酸钠；所述沉淀剂为氢氧化钠、氢氧化钾、氢氧化锂中的至少一种，其浓度为1-8mol/L；所述络合剂为氨水、硫酸铵、碳酸氢铵中的至少一种，其浓度为1-9mol/L；所述步骤（4）洗涤采用的溶液为氢氧化钠溶液。
与现有技术相比，本发明具有以下明显的有益技术效果：
（1）本发明提供的前驱体主要是以镍锰或镍铁锰氢氧化物为基体，采用共沉积方法进行外层Cu包覆，使得外层包覆元素更加均匀；共沉积Cu包覆反应结束后，通过陈化，水解进行二次Si包覆，反应更加均匀彻底；最后通过预烧使得Cu(OH)2形成CuO;两次包覆过程中均不采用络合剂进行包覆，此过程不采用络合剂的目的是使形貌表面呈疏松状态（不使用络合剂的结晶结构生长方向与添加络合剂的不一样），另外对环境友好； 包覆铜的目的是提高钠离子电池的倍率性能，包覆硅目的是防止首周充电过程中晶体结构进行崩塌形成无定形相进一步增加晶体结构的稳定性。本发明制备的前驱体的包覆层呈疏松形貌，有利于钠离子形成钠离子进出的快速通道。使制备的钠离子电池低温性能优良、容量较高、高倍率充放电、提高安全性能。
（2）本发明制备方法简单，在现有主流工艺基础上，无需增加成本，工艺适用范围广，产品结晶性好，产能高。此方法可调控外层包覆形貌及密实程度，并且可进行多元素包覆。
（3）用上述前驱体通过烧结制备出来的钠离子电池正极材料，在电池充放电过程中的晶体结构稳定不易崩塌，所制钠离子电池的倍率性能好、安全性好。
附图说明
图1为实施例1制备得到的基体前驱体材料的SEM图。
图2为实施例1制备得到包覆铜的前驱体材料SEM图。
图3为实施例1制备得到包覆铜前驱体材料的剖面能谱SEM图。
图4为实施例1制备得到的包覆硅的前驱体材料能谱SEM图。
实施例1
1、制备一种钠离子电池正极材料用前驱体，步骤如下：
（1）用硫酸镍和硫酸锰配制总金属浓度为2.0mol/L的镍、锰可溶性盐混合溶液，其中镍、锰摩尔比30：70；配制3mol/L的氨水溶液作为络合剂；配制7mol/L的氢氧化钠溶液。
（2）向反应釜中加入纯水、氨水、氢氧化钠溶液配置体积为80L的底液，调节其pH值为12.2-12.3，氨含量为0.5-1g/l，温度控制为45℃。开启搅拌装置，搅拌速度为850r, 向所述反应釜的液面下通入空气与氮气的1:5的混合气体5L/min，测试反应釜内液面氧含量2.5%,是整个反应气氛保持微氧化状态。将上述配制的镍、锰可溶性混合盐溶液与氢氧化钠溶液和氨水溶液通过精密计量泵加入到反应釜中进行反应。上述整个反应过程中，反应温度为45℃，pH值控制在11.0-11.1，混合液流量为80ml/min，氨含量为0.5-1.0g/L，粒径长至6.5um,停止反应。
反应得到的料浆经过离心, 90℃、0.5mol/L的碱水淋洗固体40分钟，然后用纯水洗涤至洗涤水的pH值为9.0，水分为8%的基体NM3070前驱体；
（3）将上述得到基体NM3070的前驱体与纯水按照质量比为1：1.5投入反应釜内，再将配制好的2.0mol/L硫酸铜溶液与氢氧化钠一定的进料速度并流进入反应釜中，维持反应的pH为8.5-8.7，沉淀剂碱溶液浓度为7mol/L，反应温度为40℃，搅拌速度600rpm，反应6h停止反应，得到外层包覆铜的氢氧化物的Cu11Ni26.7Mn62.3(OH)2前驱体；
(4)将包覆铜前驱体反应结束后，将配制的200g/L硅酸钠溶液与1%的硫酸溶液以一定流速进入反应釜中，保持反应pH为7.5-7.8，搅拌速度400 rpm，反应1h停止反应，进行固液分离，分离后经过水洗、烘干得到包覆铜硅的氢氧化物Si0.1%Cu11Ni26.7Mn62.3(OH)2前驱体；经过210℃下进行预烧得到外层包覆氧化铜前驱体；
测试：
将上述所得的Si0.1%Cu11Ni26.7Mn62.3(OH)2前驱体做扫描电镜及剖面测试，图1为其二次颗粒的扫描电镜图。图2为实施例1制备得到包覆铜的前驱体材料SEM图。图3为实施例1制备得到包覆铜前驱体材料的剖面能谱SEM图，从图3 可知Mn原子百分比为57.28%，Ni原子百分比为32.23%，Cu原子百分比为10.29%，图4为实施例1制备得到的包覆硅的前驱体材料能谱SEM图,从图4 可知Mn原子百分比为57.53%，Ni原子百分比为32.10%，Cu原子百分比为10.23%，Si原子百分比为0.32%。
用马尔文粒径测试仪测得本实施例所制备的前驱体D50为6.236μm。其比表面积为11.22m2/g，测得其振实密度为1.88g/cm3。
Claims (3)
1.一种多层包覆钠离子正极材料用前驱体的制备方法，其特征在于，包括以下步骤：
（1）配制镍锰或镍铁锰的混合盐溶液A，配制铜盐溶液B,配制硅酸盐溶液C，配制沉淀剂溶液、络合剂溶液以及酸溶液；
（2）在反应釜中用纯水、络合剂溶液、沉淀剂溶液中的一种或多种配制成反应底液，并按照体积比1：5通入空气与氮气的混合气体，且流量为5L/min；
（3）然后，在反应底液中并流通入混合盐溶液A、沉淀剂溶液和络合剂溶液进行共沉淀反应,待粒经D50长至3.0-12.0um,停止反应；整个反应过程中控制反应体系的温度为35-80℃，pH值为10-13，络合剂含量为0.1~10g/L，搅拌速度为200～1000 rpm；
（4）将步骤（3）最终得到的反应浆料进行固液分离，分离得到的固相经洗涤脱水后得到含水量为5%-15%的前驱体材料；
（5）将步骤（4）最终得到的前驱体材料与纯水按照重量比1：1-3投入反应釜内，将步骤（1）中所配制好的铜盐溶液B与沉淀剂溶液并流进入反应釜中，维持反应的pH为8-12.5，沉淀剂溶液浓度为1-8mol/L，反应温度为35-70℃，搅拌速度400-800 rpm，反应3-15h停止反应 ，得到外层包覆铜的氢氧化物的前驱体；
（6）步骤（5）中的反应结束后，将步骤（1）中配制的硅酸盐溶液C与酸溶液并流进入步骤（5）的反应釜中，保持反应pH为7-10，搅拌速度100-500 rpm，反应0.5-5h停止反应，进行固液分离，分离后经过水洗、烘干得到包覆铜硅的氢氧化物前驱体；
（7）将步骤（6）得到的包覆铜硅的氢氧化物前驱体，在150-250℃下进行预烧得到外层包覆氧化铜的SiCu1-X-Y-MNixFeyMnZ(OH)2前驱体；
所述镍锰或镍铁锰的混合盐溶液为硫酸盐、氯化盐、硝酸盐中的一种或多种，所述铜盐为硫酸铜、氯化铜中的至少一种；所述硅酸盐为硅酸钠；所述沉淀剂为氢氧化钠、氢氧化钾、氢氧化锂中的至少一种，其浓度为1-8mol/L；所述络合剂为氨水、硫酸铵、碳酸氢铵中的至少一种，其浓度为1-9mol/L；所述步骤（4）洗涤采用的溶液为氢氧化钠溶液。
2.如权利要求1所述的一种多层包覆钠离子正极材料用前驱体的制备方法所制得的前驱体，其特征在于，所述前驱体表面疏松，外层Cu包覆均匀，所述前驱体其分子式为SiCu1-X-Y-zNixFeyMnZ(OH)2，其中,0.1≤X＜0.5，0≤Y≤0.9，0＜Z≤0.8;Si占比为0.05-1.0%。
3.如权利要求1所述的一种多层包覆钠离子正极材料用前驱体的制备方法，其特征在于，所述镍锰或镍铁锰的混合盐溶液A浓度为1.0-2.5mol/L, 所述铜盐溶液B的浓度为0.5-2.0mol/L，所述硅酸盐溶液C的浓度为100-500g/L 。
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