CN109411743A - 一种高性能镍镁共掺杂尖晶石型锰酸锂材料的制备方法 - Google Patents
一种高性能镍镁共掺杂尖晶石型锰酸锂材料的制备方法 Download PDFInfo
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- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical compound [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 11
- 239000011029 spinel Substances 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 title claims description 12
- 239000011777 magnesium Substances 0.000 claims abstract description 42
- 239000000446 fuel Substances 0.000 claims abstract description 25
- 239000002019 doping agent Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000002485 combustion reaction Methods 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910013100 LiNix Inorganic materials 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims description 47
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 22
- 229940078494 nickel acetate Drugs 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 20
- 235000011285 magnesium acetate Nutrition 0.000 claims description 20
- 239000011654 magnesium acetate Substances 0.000 claims description 20
- 229940069446 magnesium acetate Drugs 0.000 claims description 20
- 235000015165 citric acid Nutrition 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 235000006748 manganese carbonate Nutrition 0.000 claims description 11
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 239000008240 homogeneous mixture Substances 0.000 claims description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 10
- 244000248349 Citrus limon Species 0.000 claims description 9
- 235000005979 Citrus limon Nutrition 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229940093474 manganese carbonate Drugs 0.000 claims description 9
- 239000011656 manganese carbonate Substances 0.000 claims description 9
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 8
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 abstract description 5
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010348 incorporation Methods 0.000 abstract description 2
- 239000011268 mixed slurry Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 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 5
- 230000005536 Jahn Teller effect Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 229910015645 LiMn Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 229910012377 LiSix Inorganic materials 0.000 description 1
- 229910018505 Ni—Mg Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- KNLQKHUBPCXPQD-UHFFFAOYSA-N manganese;sulfuric acid Chemical compound [Mn].OS(O)(=O)=O KNLQKHUBPCXPQD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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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- 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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Abstract
本发明涉及一种高性能镍镁共掺杂尖晶石型锰酸锂LiNixMg0.05Mn1.95‑xO4正极材料的制备方法。具体方法是制备掺杂剂分散液、制备燃料剂分散液、混合和合成产物等步骤,机械搅拌均匀后得到混合物浆料,然后置于瓷坩锅中,再放入预设温度为500℃的马弗炉中,在空气气氛中燃烧反应1 h,取出在空气中冷却,研磨后放入650℃马弗炉中焙烧6 h,取出在空气中冷却、研磨后得到LiNixMg0.05Mn1.95‑xO4(x=0.03‑0.15)正极材料。本发明合成的镍镁共掺杂锰酸锂正极材料的倍率性能明显优于现有的LiMn2O4。该方法具有固液水体系易混合均匀、机械搅拌混合时间短、混合浆料不需要干燥即可直接加热进行燃烧反应等优点,并且制备方法简单、快速,电化学性能优异。
Description
技术领域
本发明涉及一种高性能镍镁共掺杂尖晶石型锰酸锂材料和所述镍镁共掺杂锰酸锂LiNixMg0.05Mn1.95-xO4材料的制备方法,属于锂离子电池正极材料技术领域。
背景技术
锂离子电池 (LIB)广泛用于电动和混合动力电动汽车 (EV / HEV),还用于储能系统 (ESS)。具有三维晶体结构的尖晶石型LiMn2O4以其比容量高、成本低、环境友好和无记忆效应等优点受到了广泛的关注。然而尖晶石型LiMn2O4存在Jahn-Teller效应,导致在充放电循环过程中容量快速衰减,尤其在高温条件下(≧55℃),从而制约其发展。目前,为解决尖晶石型LiMn2O4容量衰减的研究主要集中在包覆和元素掺杂。阳离子掺杂主要集中在掺杂小含量的过渡金属元素,比如Fe、Al、Mg、Ni、Cu、Co等。结果表明,掺杂合适的阳离子取代Mn3 +,可以抑制Jahn-Teller效应,提高材料的结构稳定性。但是,Mn3+的含量减小会使初始放电比容量降低,并且还会存在一定的Jahn-Teller效应。因此,本发明通过掺杂镍和镁离子,在抑制Jahn-Teller效应的基础上,利用镍和镁离子的协同作用来提高材料的结构稳定性,改善其电化学性能。例如 Xiang M W等人,题目“Rapid synthesis of high-cyclingperformance LiMgxMn2-xO4 (x≤0.20) cathode materials by a low-temperaturesolid-state combustion method”,《Electrochemica Acta》,2014,125:524-529;Zhao HY等人,题目“A simple and mass production preferred solid-state procedure toprepare the LiSixMgxMn2-2xO4 (0≤x≤0.10) with enhanced cycling stability andrate capability”,《Journal of Alloys and Compounds》,2016,671:304-311;Zhang H等人,题目“Structure and performance of dual-doped LiMn2O4 cathode materialsprepared via microwave synthesis method”,《Electrochemica Acta》,2014,125:225-231;Chen M F等人,题目“Ni, Mo co-doped lithium manganate with significantlyenhanced discharge capacity and cycling stability”,《Electrochemica Acta》,2016,206:356-365;Zhao H Y等人,题目“Enhanced Cycling Stability of LiCuxMn1.95- xSi0.05O4 Cathode Material Obtained by Solid-State Method”,《Materials》,2018,11:1302。
CN106784657A公开了一种钠和铁共掺杂制备高性能锰酸锂正极材料的方法,其制备方法是(1)锰源前驱体的制备;(2)将锰源、锂源、钠源和铁源置于烧杯中加入100 mL无水乙醇震荡60 min后干燥,然后再研磨10-120 min。(3)将研磨物预烧结2-10 h后,再在650~850℃马弗炉中煅烧10-30 h,即得钠和铁双掺杂的锰酸锂正极材料。CN106450285A公开了一种钠、镁双掺杂提高锰酸锂正极材料电化学性能的制备方法,其制备方法是(1)将硫酸锰、碳酸氢铵分别溶于100-500 mL去离子水中;(2)将碳酸氢铵溶液分3次缓慢滴加到硫酸锰溶液中,得到的悬浊液经搅拌、陈化、抽滤和洗涤后干燥8-12 h得到碳酸锰粉末;(3)将碳酸锰粉末烧结得到二氧化锰黑色粉末;(4)将锂源、锰源、钠源和镁源置于研磨中充分研磨后,在650-850℃马弗炉中烧结10-24 h,得到Li1-xNaxMgyMn2-yO4正极材料。
上述方法都存在加工工艺复杂、反应时间长、反应温度高等缺陷。因此,针对这些技术缺陷,本发明人在总结现有技术基础之上,通过大量实验研究与分析,完成了本发明。
发明内容
本发明采用固液水混合体系,机械搅拌混合时间短,反应混合物浆料不需要干燥,直接加热进行燃烧反应,制备方法简单、快速,并且电化学性能优异,目的是提供一种抑制Jahn-Teller效应、增强尖晶石型锰酸锂结构稳定性的基础上,制备一种结构稳定、高倍率性能镍镁共掺杂的尖晶石型锰酸锂正极材料。
本发明涉及一种高性能镍镁共掺杂尖晶石型锰酸锂材料的制备方法。
该合成方法以碳酸锂为锂源、碳酸锰为锰源、醋酸镍为镍掺杂剂和醋酸镁为镁掺杂剂,按照化学计量比Li: Mn: Ni: Mg =1: (1.95-x) : x : 0.05 (x=0.03-0.15)配比原料,添加原料总质量的5 wt.%柠檬酸为燃料。其特征在于该方法的步骤如下:
A、制备掺杂剂分散液
按照化学计量比Li: Mn: Ni: Mg =1: (1.95-x) : x : 0.05 (x=0.03-0.15)称量固体醋酸镍和醋酸镁,然后以克计醋酸镍和醋酸镁的总质量,以毫升计去离子水的体积,按照质量与体积比为1:5-10,将醋酸镍和醋酸镁添加到去离子水中,使醋酸镍和醋酸镁完全溶解,得到均匀的镍镁掺杂剂分散液;
B、制备燃料剂分散液
按照以克计柠檬酸和以毫升计去离子水的比为1: 1-5,将柠檬酸燃料加到去离子水中,充分溶解得到一种均匀的燃料剂分散液;
C、混合
按照化学计量比Li: Mn =1: (1.95-x) (x=0.03-0.15)称量固体碳酸锂和碳酸锰置于烧杯中,然后按照化学计量比Li: Mn: Ni: Mg =1: (1.95-x) : x : 0.05 (x=0.03-0.15),准确加入以毫升计的镍镁掺杂剂分散液(步骤A所得),再准确加入以毫升计的柠檬酸燃料剂分散液(步骤B所得),最后机械搅拌一定时间得到一种均匀混合物浆料;
D、合成产物
将所得到的均匀混合物浆料移入瓷坩埚中,然后将装有混合物浆料的瓷坩埚直接放入预设温度为500 ℃马弗炉,在空气气氛中加热直至发生燃烧反应1 h,取出自然冷却,得到黑色燃烧产物。然后,把焙烧产物研磨后放入650 ℃马弗炉,在空气气氛中焙烧6 h,取出在空气中自然冷却、研磨后得到产物LiNixMg0.05Mn1.95-xO4 (x=0.03-0.15)正极材料粉末。
采用X射线衍射分析仪,例如Bruker公司的D8 ADVANCE型X射线衍射仪,以Cu-Kα靶为辐射源,在工作电压40kV、工作电流40mA、扫描范围2θ为10-70°与扫描速率4°/min的条件下测试分析,其结果列于附图1。通过材料测试的XRD与LiMn2O4标准PDF卡(JCPDS No. 35-0782)对比分析确定表明该产物均为单相,无杂质,具有尖晶石型结构,空间点群为Fd3m,具体参见附图1。
本发明合成方法合成得到的产物进行了常规电子显微镜分析。采用美国FEI公司的NOVA NANOSEM 450型场发射扫描电子显微镜与TEM,JEM-2100透射电子显微镜,在常规的条件下测试,Ni-Mg共掺杂LiNi0.03Mg0.05Mn1.92O4材料的扫描电子显微镜结果列于附图2 (a)中。附图2 (a)表明,LiNi0.03Mg0.05Mn1.92O4样品的颗粒尺寸在120-220 nm之间,其透射电子显微镜结果列于附图2 (b)和(c)中。
采用Land恒电流充放电测试系统在1 C倍率与温度25℃下测试充放电1000次,本发明实施例1与对比实施例1的充放电循环性能参见附图3 (a)。
采用Land恒电流充放电测试系统在0.5、1、2、5、8、10和0.5C倍率与温度25 ℃时分别各测试充放电10次,本发明实施例1与对比实施例1的倍率性能参见附图3 (b)。
采用Land恒电流充放电测试系统在20 C倍率与温度25℃下测试充放电1000次,本发明实施例1与对比实施例1的高倍率充放电循环性能参见附图3 (c)。
采用Land恒电流充放电测试系统在1 C倍率与温度55℃下测试充放电500次,本发明实施例1与对比实施例1的高温充放电循环性能参见附图3 (d)。
附图说明
图1是实施例1得到的镍镁离子共掺杂前后锰酸锂正极材料的XRD图。
图2是实施例1得到的LiNi0.03Mg0.05Mn1.92O4正极材料的扫描电子显微镜(SEM)和透射电子显微镜 (TEM)图。图中:
(a) LiNi0.03Mg0.05Mn1.92O4正极材料的扫描电子显微镜图;
(b) LiNi0.03Mg0.05Mn1.92O4正极材料的透射电子显微镜图;
(c) LiNi0.03Mg0.05Mn1.92O4正极材料的高分辨透射电子显微镜图。
图3是实施例1得到的镍镁离子共掺杂前后锰酸锂正极材料的电性能图。图中:
(a)采用恒电流充放电测试在1 C、25℃下的循环性能图;
(b)采用恒电流充放电测试在0.5、1、2、5、8、10和0.5C,25℃下的倍率电性能图;
(c)采用恒电流充放电测试在20 C、25℃下的循环性能图;
(d)采用恒电流充放电测试在1 C、55℃下的循环性能图。
具体实施方式
通过下述实施例将能够更好地理解本发明。
实施例1:本发明镍镁掺杂锰酸锂正极材料合成
该实施例的实施步骤如下:
该合成方法以碳酸锂为锂源、碳酸锰为锰源、醋酸镍为镍掺杂剂和醋酸镁为镁掺杂剂,按照化学计量比Li: Mn: Ni: Mg =1: 1.92: 0.03: 0.05配比原料,添加原料总质量的5wt.%柠檬酸为燃料。其特征在于该方法的步骤如下:
A、制备掺杂剂分散液
按照化学计量比Li: Mn: Ni: Mg =1: 1.92 : 0.03 : 0.05称量固体醋酸镍和醋酸镁,然后以克计准确称量醋酸镍和醋酸镁的总质量,以毫升计去离子水的体积,按照质量与体积比为1:6,将醋酸镍和醋酸镁添加到去离子水中,使醋酸镍和醋酸镁完全溶解,得到均匀的镍镁掺杂剂分散液;
B、制备燃料剂分散液
按照以克计柠檬酸和以毫升计去离子水的比为1: 4,将柠檬酸燃料加到去离子水中,充分溶解得到一种均匀的燃料剂分散液;
C、混合
按照化学计量比Li: Mn =1: 1.92称量0.7959 g碳酸锂和4.7051g碳酸锰置于烧杯中,然后按照化学计量比Li: Mn: Ni: Mg =1: 1.92 : 0.03 : 0.05,准确加入以毫升计的镍镁掺杂剂分散液(含0.1624 g醋酸镍和0.2332 g醋酸镁),再准确加入以毫升计的柠檬酸燃料剂分散液(含0.3000 g柠檬酸),机械搅拌1 h后得到一种均匀混合物浆料;
D、合成产物
将所得到的均匀混合物浆料移入瓷坩埚中,然后将装有混合物浆料的瓷坩埚直接放入预设温度为500 ℃马弗炉,在空气气氛中加热直至发生燃烧反应1 h,取出自然冷却,得到黑色燃烧产物。然后,把焙烧产物研磨后放入650 ℃马弗炉,在空气气氛中焙烧6 h,取出在空气中自然冷却、研磨后得到产物LiNi0.03Mg0.05Mn1.92O4正极材料粉末。
实施例2:本发明镍、镁掺杂锰酸锂正极材料合成
该实施例的实施步骤如下:
以碳酸锂为锂源、碳酸锰为锰源、醋酸镍为镍掺杂剂和醋酸镁为镁掺杂剂,按照化学计量比Li: Mn: Ni: Mg =1: 1.90: 0.05: 0.05配比原料,添加原料总质量的5 wt.%柠檬酸为燃料。其特征在于该方法的步骤如下:
A、制备掺杂剂分散液
按照化学计量比Li: Mn: Ni: Mg =1: 1.90 : 0.05 : 0.05称量固体醋酸镍和醋酸镁,然后以克计准确称量醋酸镍和醋酸镁的总质量,以毫升计去离子水的体积,按照质量与体积比为1:7,将醋酸镍和醋酸镁添加到去离子水中,使醋酸镍和醋酸镁完全溶解,得到均匀的镍镁掺杂剂分散液;
B、制备燃料剂分散液
按照以克计柠檬酸和以毫升计去离子水的比为1: 3,将柠檬酸燃料加到去离子水中,充分溶解得到一种均匀的燃料剂分散液;
C、混合
按照化学计量比Li: Mn =1: 1.90称量0.7959 g碳酸锂和4.7051 g碳酸锰置于烧杯中,然后按照化学计量比Li: Mn: Ni: Mg =1: 1.90 : 0.05 : 0.05,准确加入以毫升计的镍镁掺杂剂分散液(含0.2681 g醋酸镍和0.2310 g醋酸镁),再准确加入以毫升计的柠檬酸燃料剂分散液(含0.3000 g柠檬酸),机械搅拌1.5 h后得到一种均匀混合物浆料;
D、合成产物
将所得到的均匀混合物浆料移入瓷坩埚中,然后将装有混合物浆料的瓷坩埚直接放入预设温度为500 ℃马弗炉,在空气气氛中加热直至发生燃烧反应1 h,取出自然冷却,得到黑色燃烧产物。然后,把焙烧产物研磨后放入650 ℃马弗炉,在空气气氛中焙烧6 h,取出在空气中自然冷却、研磨后得到产物LiNi0.05Mg0.05Mn1.92O4正极材料粉末。
对比实施例1:本发明未掺杂尖晶石型锰酸锂正极材料合成
以碳酸锂和碳酸锰为原料,按照化学计量比Li: Mn =1: 2配比原料,添加原料总质量的5 wt.%柠檬酸为燃料。该实施例的实施步骤如下:
A、制备燃料剂分散液
按照以克计柠檬酸和以毫升计去离子水的比为1: 5,将柠檬酸加到去离子水中,充分溶解得到一种均匀的柠檬酸燃料剂分散液;
B、混合
按照化学计量比Li: Mn =1: 2称取0.8307 g碳酸锂和5.1693 g碳酸锰置于烧杯中,然后加入以毫升计的柠檬酸燃料剂分散液(含0.3000 g柠檬酸),并添加适量去离子水,机械搅拌1 h均匀后得到一种反应混合物浆料;
C、合成产物
将所得到的均匀混合物浆料移入瓷坩埚中,然后将装有混合物浆料的瓷坩埚直接放入预设温度为500 ℃马弗炉,在空气气氛中加热直至发生燃烧反应1 h,取出自然冷却,得到黑色燃烧产物。然后,把焙烧产物研磨后放入650 ℃马弗炉,在空气气氛中焙烧6 h,取出在空气中自然冷却、研磨后得到产物LiMn2O4正极材料粉末。
通过比较对比实施例1与实施例1合成正极材料,本发明合成的镍镁共掺杂LiNixMg0.05Mn1.95-xO4(x=0.03-0.15)正极材料的循环性能和倍率明显优于对比例实施例1合成的LiMn2O4,表明本发明具有很好的电化学性能。
Claims (7)
1.一种高性能镍镁共掺杂尖晶石型锰酸锂材料的制备方法,以碳酸锂为锂源、碳酸锰为锰源、醋酸镍为镍掺杂剂和醋酸镁为镁掺杂剂,按照化学计量比Li: Mn: Ni: Mg =1:(1.95-x) : x : 0.05 (x=0.03-0.15)配比原料,添加原料总质量的5 wt.%柠檬酸为燃料。其特征在于该方法的步骤如下:
A、制备掺杂剂分散液
按照化学计量比Li: Mn: Ni: Mg =1: (1.95-x) : x : 0.05 (x=0.03-0.15)称量固体醋酸镍和醋酸镁,然后以克计醋酸镍和醋酸镁的总质量,以毫升计去离子水的体积,按照质量与体积比为1:5-10,将醋酸镍和醋酸镁添加到去离子水中,使醋酸镍和醋酸镁完全溶解,得到均匀的镍镁掺杂剂分散液。
B、制备燃料剂分散液
按照以克计柠檬酸和以毫升计去离子水的比为1: 1-5,将柠檬酸燃料加到去离子水中,充分溶解得到一种均匀的燃料剂分散液。
C、混合
按照化学计量比Li: Mn =1: (1.95-x) (x=0.03-0.15)称量固体碳酸锂和碳酸锰置于烧杯中,然后按照化学计量比Li: Mn: Ni: Mg =1: (1.95-x) : x : 0.05 (x=0.03-0.15),准确加入以毫升计的镍镁掺杂剂分散液(步骤A所得),再准确加入以毫升计的柠檬酸燃料剂分散液(步骤B所得),最后机械搅拌一定时间得到一种均匀混合物浆料。
D、合成产物
将所得到的均匀混合物浆料移入瓷坩埚中,然后将装有混合物浆料的瓷坩埚直接放入预设温度为500 ℃马弗炉,在空气气氛中加热直至发生燃烧反应1 h,取出自然冷却,得到黑色燃烧产物。然后,把焙烧产物研磨后放入650 ℃马弗炉,在空气气氛中焙烧6 h,取出在空气中自然冷却、研磨后得到产物LiNixMg0.05Mn1.95-xO4 (x=0.03-0.15)正极材料粉末。
2.根据权利要求1所述的合成方法,其特征在于所述加入以毫升计的柠檬酸燃料剂分散液的体积中需含有原料总质量5 wt.%柠檬酸。
3.根据权利要求1所述的合成方法,其特征在于所述机械搅拌时间为1-2h。
4.根据权利要求1所述的合成方法,其特征在于所述均匀混合物浆料不需要干燥,直接在瓷坩埚中加热直至发生燃烧反应。
5.根据权利要求1-4中任一项权利要求所述制备方法合成得到的材料为LiNixMg0.05Mn1.95-xO4 (x=0.03-0.15)正极材料。
6.根据权利要求5所述的LiNixMg0.05Mn1.95-xO4 (x=0.03-0.15)正极材料,其特征在于具有尖晶石型结构,空间点群为Fd3m,其形貌为多面体,颗粒尺寸在120-220nm之间。
7.根据权利要求4所述的LiNixMg0.05Mn1.95-xO4 (x=0.03-0.15)正极材料,其特征在于在充放电倍率为1 C时它具有下述电性能:
首次放电比容量为74.2~112.3 mAh·g-1;
第1000次放电比容量为47.8~82.8 mAh·g-1。
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