CN115763947B - 安时级钠离子软包电池 - Google Patents
安时级钠离子软包电池 Download PDFInfo
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- CN115763947B CN115763947B CN202211383081.9A CN202211383081A CN115763947B CN 115763947 B CN115763947 B CN 115763947B CN 202211383081 A CN202211383081 A CN 202211383081A CN 115763947 B CN115763947 B CN 115763947B
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 35
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000011734 sodium Substances 0.000 claims abstract description 37
- 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 claims abstract description 34
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 238000005520 cutting process Methods 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000005056 compaction Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011888 foil Substances 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- AASUFOVSZUIILF-UHFFFAOYSA-N diphenylmethanone;sodium Chemical compound [Na].C=1C=CC=CC=1C(=O)C1=CC=CC=C1 AASUFOVSZUIILF-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000010406 cathode material Substances 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 4
- -1 sodium hexafluorophosphate Chemical group 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical group CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims 1
- 238000003475 lamination Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 238000012856 packing Methods 0.000 claims 1
- 239000002985 plastic film Substances 0.000 abstract description 6
- 229920006255 plastic film Polymers 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 4
- 239000011149 active material Substances 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000009461 vacuum packaging Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 239000012047 saturated solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
本发明涉及一种钠离子软包电池,属于新能源材料与器件技术领域,包括正极极片、隔膜、预钠负极极片、电解液、极耳、铝塑膜包装,以Z字形方式依次将1~30片正极极片、2~31片预钠负极极片叠片,加入电解液并封装得到,其特征在于:所述正极极片中含有O3层状氧化物正极材料,化学式为NaaNibZncFedMneTi(1‑b‑c‑d‑e)O2,0.8≤a≤1,0.2<b≤0.5,0<c≤0.1,0<d≤0.2,0.2<e≤0.5,所述预钠负极极片中含有硬碳负极材料,所述正极极片双面密度为28‑33mg/cm2;所述负极极片双面密度为14‑16mg/cm2,电池容量为0.1‑10Ah。本发明钠离子软包电池循环寿命长,可广泛应用于新能源汽车,以及大规模储能等领域。
Description
技术领域
本发明属于新能源材料与器件技术领域,具体涉及一种安时级别钠离子软包电池。
背景技术
钠资源在地球上储量非常丰富,元素含量约为23000ppm(锂含量仅约17ppm),且分布于全球各地,不受地域限制。所以在资源方面,钠离子电池比锂离子电池具有更大的优势。研究钠离子电池可避免锂短缺导致的新能源电池发展存在的资源问题,并可逐步取代环境污染严重的铅酸电池,还可以沿用现有锂离子电池的材料及电池生产工序和生产装备,被认为是大规模储能领域的变革性技术之一,其产业化前景相当乐观,具有重要的经济价值和战略意义。
近年来,不同技术路线的钠离子电池已被广泛研究。同时,大规模储能领域的快速发展对低成本、高容量、长循环寿命的钠离子电池需求也日益增加。当前钠离子电池的研究主要集中在实验室阶段的纽扣小电池上,不能直观反映出电池体系内部存在的真实问题,缺少专利对最常见的软包电池进行研究。因此,开发和优化钠离子软包电池的组装工艺对其商业化应用具有重要意义。
CN114976211A公开了一种钠离子软包电池,该专利基于硫酸盐正极及硬碳负极,软包电池仅能几十毫安时的容量,且循环稳定性较差。正负极的压实密度不高,难以进行大容量软包电池的组装。同时对于关键的补钠技术及正负极容量匹配问题没有优化。
发明内容
本发明的目的是克服现有技术的问题,提供一种钠离子软包电池,该软包电池选用O3层状氧化物作为正极材料,商业化硬碳为负极材料,结合新型化学预钠硬碳负极可弥补钠离子的不可逆损失。同时,对钠离子软包电池的组装工艺也进行了优化,选用较高的压实密度能够实现大容量软包电池的组装,优化正负极的面密度以及容量比,可以实现不同安时级别钠离子软包电池的稳定运行。
实现本发明目的的技术方案如下:
本发明提供了一种安时级别钠离子软包电池,包括正极极片、隔膜、预钠负极极片、电解液、极耳、铝塑膜包装,以Z字形方式依次将1~30片正极极片、2~31片预钠负极极片叠片,加入电解液并封装得到,其特征在于:所述正极极片中含有O3层状氧化物正极材料,化学式为NaaNibZncFedMneTi(1-b-c-d-e)O2,0.8≤a≤1,0.2<b≤0.5,0<c≤0.1,0<d≤0.2,0.2<e≤0.5,所述预钠负极极片中含有硬碳负极材料,所述正极极片单面密度为14-18mg/cm2,双面密度为28-36mg/cm2;所述负极极片单面密度为7-10mg/cm2,双面密度为14-20mg/cm2,正极极片模切尺寸为53.5mm~83mm*83.5mm~163mm,负极极片模切尺寸为55.5mm~85mm*85.5mm~165mm,电池容量为0.1-10Ah。
进一步地,所述O3层状氧化物正极材料的制备方法为:按1:0.3:0.1:0.1:0.3:0.2摩尔计量比例称取碳酸钠、氧化镍、氧化锌、三氧化二铁、二氧化锰、二氧化钛,粉碎混合后,在空气中煅烧,煅烧温度为800-1100℃,升温速率为1~5℃/min,煅烧时间为12-20小时。
进一步地,所述正极极片的制备方法为将O3层状氧化物正极材料、Super-p、PVDF按照93:3:4的质量比来称取,将上述三种材料分散在N-甲基吡咯烷酮溶剂中,混合均匀后涂布到铝箔上,80~100℃真空条件下干燥10~15h,获得正极极片,将正极极片辊压至压实密度为2.6g/cm3~3.0g/cm3,再模切至尺寸53.5mm~83mm*83.5mm~163mm。优选地,正极极片模切尺寸为163*83mm和83.5*53.5mm的一种。
进一步地,所述预钠负极极片的制备方法为将硬碳负极材料、Super-p、丁苯橡胶、羧甲基纤维素按照93:3:2:2的质量比来称取,将上述四种材料分散在纯水中,混合均匀后涂布到铝箔上,70~90℃真空条件下干燥10~15h,获得负极极片,将负极极片辊压至压实密度为1.0g/cm3~1.5g/cm3,再模切至尺寸55.5mm~85mm*85.5mm~165mm,再将负极极片在二苯甲酮-钠溶液中浸泡2~4h,后使用四氢呋喃溶液清洗,70~90℃真空条件下干燥8~12h,获得预钠负极极片。优选地,负极极片模切尺寸为165.5*85.5mm和85.5*55.5mm的一种。
进一步地,预钠溶液的溶剂为乙二醇二甲醚,溶质为二苯甲酮与钠,溶质浓度为0.001-2mol/L。制备方法为:先将二苯甲酮加入乙二醇二甲醚中,再加入钠块,形成二苯甲酮与钠的饱和溶液。
进一步地,所述电解液的浓度为1mol/L,溶质为六氟磷酸钠,溶剂为碳酸甲乙酯、碳酸乙烯酯和碳酸二甲酯以1:1:1体积比混合的混合液。
本发明的优点:
1.本发明利用O3层状氧化物正极材料优异的稳定性,可实现软包电池优异的长循环稳定性。同时,新型化学预钠硬碳负极可弥补电芯首圈钠离子的不可逆损失,从而获得较高的首圈库伦效率。选用合适的压实密度可以实现大容量电池的组装,同时可以减少电解液的加入量,有利于电池的长循环稳定性。
2.本发明提供了不同安时级别钠离子电池及其制备方法,组装工艺易于操作,利于大规模化生产;软包电池成本低廉,循环寿命长,可广泛应用于新能源汽车,以及大规模储能等领域。
附图说明
图1是实施例1所示软包电池的首圈充放电曲线;
图2是实施例1所示软包电池的容量循环对比图;
图3是实施例2所示软包电池的首圈充放电曲线;
图4是实施例2所示软包电池的容量循环对比图;
图5是实施例3所示软包电池的首圈充放电曲线;
图6是实施例3所示软包电池的容量循环对比图;
图7是实施例4所示软包电池的首圈充放电曲线;
图8是实施例1-4所示软包电池的实物图。
具体实施方式
下面结合附图对本发明进行详细、完整地描述。
实施例1:
本实施例提供一种百毫安时级钠离子软包电池,正极材料为O3层状氧化物,负极为商业化硬碳。
正极极片制备:将活性材料、导电剂、粘结剂按93:3:4的质量比混合,即称取1000gO3层状氧化物正极材料32gSuper-p和43g聚偏氟乙烯控制N-甲基吡咯烷酮溶剂的添加量,在粘度为8000cps时双面涂布到铝箔上,90℃真空条件下干燥12h,单位面积上活性材料的质量为29-32mg/cm2。其中O3层状氧化物正极材料的制备方法为:将碳酸钠、氧化镍、氧化锌、三氧化二铁、二氧化锰及二氧化钛按1:0.3:0.1:0.1:0.3:0.2摩尔计量比例粉碎混合,在空气中煅烧,煅烧温度为900℃,升温速率为5℃/min,煅烧时间为15小时。
负极极片制备:将活性材料、导电剂、粘结剂1、粘结剂2按93:3:2:2的质量比混合,即称取600gO3层状氧化物正极材料,19.5gSuper-p,12.9g丁苯橡胶及12.9g羧甲基纤维素,控制去离子水的添加量,在粘度为4500cps时双面涂布到铝箔上,90℃真空条件下干燥12h,单位面积上活性材料的质量为14-18mg/cm2。
正负极片的辊压:选择130微米的辊缝对硬碳负极片进行辊压,得到的负极片压实密度为1.02-1.1g/cm3,选择110微米的辊缝对正极极片进行辊压,得到的正极片压实密度为2.6-2.8g/cm3。
极片模切:将正极片模切成宽53.5mm,长83.5mm,极耳长度为8mm,宽度为6mm的正极极片;将负极片模切成宽55.5mm,长85.5mm,极耳长度为8mm,宽度为6mm的负极极片。
负极预钠:在惰性气氛保护下,将模切后的负极极片放入浓度为1mol/L的二苯甲酮-钠的乙二醇二甲醚溶液中,2h后取出并用四氢呋喃洗涤三遍,80℃真空条件下干燥12h,获得预钠后的负极极片。
软包电池制备:将4片正极极片、celgard2400隔膜、5片预钠后负极极片按Z字形顺序依次叠片,使用专用胶带固定。选择0.1*8*60mm的铝极耳对正负极片进行焊接在外部用铝塑膜封闭,在80℃真空条件下干燥8h控制水分在20ppm以下,后注入4ml1MNaPF6/EC+EMC+DMC(1:1:1,体积比)电解液,在静置机内进行3次真空、充气操作,将电芯真空封装并静置24h后获得钠离子软包电池。
软包电池化成:以0.02C电流充电至3.4V,0.05C充电至3.8V后常温搁置24h,再以0.1C充电到4.0V。然后以0.2C电流恒流放电至终止电压1.8V,完成电池的化成。
软包电池二封与测试:将化成结束的软包电池的气囊剪掉,进行真空二封;软包电池在0.1C-2C倍率下进行循环测试,充放电截止电压为1.8V和3.9V。
图8所示为组装的软包电池实物图,该软包电池在1C倍率条件下循环性能如图1,2所示,软包电池首圈放电容量为205mAh,经过900圈循环后仍有185mAh的放电容量。
实施例2:
本实施例提供一种1安时级钠离子软包电池,正极材料为O3层状氧化物,负极为商业化硬碳。
正极极片制备:将活性材料、导电剂、粘结剂按93:3:4的质量比混合,即称取1000gO3层状氧化物正极材料32gSuper-p和43g聚偏氟乙烯控制N-甲基吡咯烷酮溶剂的添加量,在粘度为8000cps时双面涂布到铝箔上,90℃真空条件下干燥12h,单位面积上活性材料的质量为29-32mg/cm2。其中O3层状氧化物正极材料的制备方法为:将碳酸钠、氧化镍、氧化锌、三氧化二铁、二氧化锰及二氧化钛按1:0.3:0.1:0.1:0.3:0.2摩尔计量比例粉碎混合,在空气中煅烧,煅烧温度为900℃,升温速率为5℃/min,煅烧时间为15小时。
负极极片制备:将活性材料、导电剂、粘结剂1、粘结剂2按93:3:2:2的质量比混合,即称取600gO3层状氧化物正极材料,19.5gSuper-p,12.9g丁苯橡胶及12.9g羧甲基纤维素,控制去离子水的添加量,在粘度为4500cps时双面涂布到铝箔上,90℃真空条件下干燥12h,单位面积上活性材料的质量为14-18mg/cm2。
正负极片的辊压:选择130微米的辊缝对硬碳负极片进行辊压,得到的负极片压实密度为1.02-1.1g/cm3,选择110微米的辊缝对正极极片进行辊压,得到的正极片压实密度为2.6-2.8g/cm3。
极片模切:将正极片模切成宽53.5mm,长83.5mm,极耳长度为8mm,宽度为6mm的正极极片;将负极片模切成宽55.5mm,长85.5mm,极耳长度为8mm,宽度为6mm的负极极片。
负极预钠:在惰性气氛保护下,将模切后的负极极片放入浓度为1mol/L的二苯甲酮-钠的乙二醇二甲醚溶液中,2h后取出并用四氢呋喃洗涤三遍,80℃真空条件下干燥12h,获得预钠后的负极极片。
软包电池制备:将11片正极极片、celgard2400隔膜、12片预钠后负极极片按Z字形顺序依次叠片,使用专用胶带固定。选择0.1*8*60mm的铝极耳对正负极片进行焊接在外部用铝塑膜封闭,在80℃真空条件下干燥8h,控制水分在20ppm以下,后注入8ml1MNaPF6/EC+EMC+DMC(1:1:1,体积比)电解液,在静置机内进行3次真空、充气操作,将电芯真空封装并静置24h后获得钠离子软包电池。
软包电池化成:以0.02C电流充电至3.4V,0.05C充电至3.8V后常温搁置24h,再以0.1C充电到4.0V。然后以0.2C电流恒流放电至终止电压1.8V,完成电池的化成。
软包电池二封与测试:将化成结束的软包电池的气囊剪掉,进行真空二封;软包电池在0.1C-2C倍率下进行循环测试,充放电截止电压为1.8V和3.9V。
图8所示为组装的软包电池实物图,该软包电池在0.1C倍率条件下循环性能如图3,4所示,软包电池首圈放电容量为1470mAh,经过110圈循环后仍有1400mAh的放电容量。
实施例3:
本实施例提供一种5安时级钠离子软包电池,正极材料为O3层状氧化物,负极为商业化硬碳。
正极极片制备:将活性材料、导电剂、粘结剂按93:3:4的质量比混合,即称取1000gO3层状氧化物正极材料32gSuper-p和43g聚偏氟乙烯控制N-甲基吡咯烷酮溶剂的添加量,在粘度为8000cps时双面涂布到铝箔上,90℃真空条件下干燥12h,单位面积上活性材料的质量为29-32mg/cm2。其中O3层状氧化物正极材料的制备方法为:将碳酸钠、氧化镍、氧化锌、三氧化二铁、二氧化锰及二氧化钛按1:0.3:0.1:0.1:0.3:0.2摩尔计量比例粉碎混合,在空气中煅烧,煅烧温度为900℃,升温速率为5℃/min,煅烧时间为15小时。
负极极片制备:将活性材料、导电剂、粘结剂1、粘结剂2按93:3:2:2的质量比混合,即称取600gO3层状氧化物正极材料,19.5gSuper-p,12.9g丁苯橡胶及12.9g羧甲基纤维素,控制去离子水的添加量,在粘度为4500cps时双面涂布到铝箔上,90℃真空条件下干燥12h,单位面积上活性材料的质量为14-18mg/cm2。
正负极片的辊压:选择130微米的辊缝对硬碳负极片进行辊压,得到的负极片压实密度为1.02-1.1g/cm3,选择110微米的辊缝对正极极片进行辊压,得到的正极片压实密度为2.6-2.8g/cm3。
极片模切:正极片模切成宽83mm,长163mm,极耳长度为8mm,宽度为6mm的正极极片;将负极片模切成宽85.5mm,长165.5mm,极耳长度为8mm,宽度为6mm的负极极片。
负极预钠:在惰性气氛保护下,将模切后的负极极片放入浓度为1mol/L的二苯甲酮-钠的乙二醇二甲醚溶液中,2h后取出并用四氢呋喃洗涤三遍,80℃真空条件下干燥12h,获得预钠后的负极极片。
软包电池制备:将14片正极极片、celgard2400隔膜、15片预钠后负极极片按Z字形顺序依次叠片,使用专用胶带固定。选择0.15*12*60mm的铝极耳对正负极片进行焊接,在外部用铝塑膜封闭,在80℃真空条件下干燥8h,控制水分在20ppm以下,后注入25ml1MNaPF6/EC+EMC+DMC(1:1:1,体积比)电解液,在静置机内进行3次真空、充气操作,将电芯真空封装并静置24h后获得钠离子软包电池。
软包电池化成:以0.02C电流充电至3.4V,0.05C充电至3.8V后常温搁置24h,再以0.1C充电到4.0V。然后以0.2C电流恒流放电至终止电压1.8V,完成电池的化成。
软包电池二封与测试:将化成结束的软包电池的气囊剪掉,进行真空二封;软包电池在0.1C-2C倍率下进行循环测试,充放电截止电压为1.8V和3.9V。
图8所示为组装的软包电池实物图,该软包电池在0.2C倍率条件下循环性能如图5,6所示,软包电池首圈放电容量为5770mAh,经过900圈循环后仍有4880mAh的放电容量。
实施例4:
本实施例提供一种8安时级钠离子软包电池,正极材料为O3层状氧化物,负极为商业化硬碳。
正极极片制备:将活性材料、导电剂、粘结剂按93:3:4的质量比混合,即称取1000gO3层状氧化物正极材料32gSuper-p和43g聚偏氟乙烯控制N-甲基吡咯烷酮溶剂的添加量,在粘度为8000cps时双面涂布到铝箔上,90℃真空条件下干燥12h,单位面积上活性材料的质量为29-32mg/cm2。其中O3层状氧化物正极材料的制备方法为:将碳酸钠、氧化镍、氧化锌、三氧化二铁、二氧化锰及二氧化钛按1:0.3:0.1:0.1:0.3:0.2摩尔计量比例粉碎混合,在空气中煅烧,煅烧温度为900℃,升温速率为5℃/min,煅烧时间为15小时。
负极极片制备:将活性材料、导电剂、粘结剂1、粘结剂2按93:3:2:2的质量比混合,即称取600gO3层状氧化物正极材料,19.5gSuper-p,12.9g丁苯橡胶及12.9g羧甲基纤维素,控制去离子水的添加量,在粘度为4500cps时双面涂布到铝箔上,90℃真空条件下干燥12h,单位面积上活性材料的质量为14-18mg/cm2。
正负极片的辊压:选择130微米的辊缝对硬碳负极片进行辊压,得到的负极片压实密度为1.02-1.1g/cm3,选择110微米的辊缝对正极极片进行辊压,得到的正极片压实密度为2.6-2.8g/cm3。
极片模切:正极片模切成宽83mm,长163mm,极耳长度为8mm,宽度为6mm的正极极片;将负极片模切成宽85.5mm,长165.5mm,极耳长度为8mm,宽度为6mm的负极极片。
负极预钠:在惰性气氛保护下,将模切后的负极极片放入浓度为1mol/L的二苯甲酮-钠的乙二醇二甲醚溶液中,2h后取出并用四氢呋喃洗涤三遍,80℃真空条件下干燥12h,获得预钠后的负极极片。
软包电池制备:将23片正极极片、celgard2400隔膜、24片预钠后负极极片按Z字形顺序依次叠片,使用专用胶带固定。选择0.15*12*60mm的铝极耳对正负极片进行焊接,在外部用铝塑膜封闭,在80℃真空条件下干燥8h,控制水分在20ppm以下,后注入45ml1MNaPF6/EC+EMC+DMC(1:1:1,体积比)电解液,在静置机内进行3次真空、充气操作,将电芯真空封装并静置24h后获得钠离子软包电池。
软包电池化成:以0.02C电流充电至3.4V,0.05C充电至3.8V后常温搁置24h,再以0.1C充电到4.0V。然后以0.2C电流恒流放电至终止电压1.8V,完成电池的化成。
软包电池二封与测试:将化成结束的软包电池的气囊剪掉,进行真空二封;软包电池在0.1C-2C倍率下进行循环测试,充放电截止电压为1.8V和3.9V。
图8所示为组装的软包电池实物图,该软包电池在0.1C倍率条件下电化学性能如图7所示,软包电池首圈放电容量为8100mAh。
以上所述的仅是本发明的优选实施方式,应当指出,对于本领域的普通技术人员来说,在不脱离发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。
Claims (6)
1.一种安时级别钠离子软包电池,包括正极极片、隔膜、预钠负极极片、电解液、极耳、铝塑膜包装,以Z字形方式依次将1~30片正极极片、2~31片预钠负极极片叠片,加入电解液并封装得到,其特征在于:所述正极极片中含有O3层状氧化物正极材料,化学式为NaaNibZncFedMneTi(1-b-c-d-e)O2,0.8≤a≤1,0.2<b≤0.5,0<c≤0.1,0<d≤0.2,0.2<e≤0.5,所述预钠负极极片中含有硬碳负极材料,所述正极极片双面密度为28-33mg/cm2;所述负极极片双面密度为14-16mg/cm2,正极极片压实密度为2.6g/cm3~3.0g/cm3,模切尺寸为53.5mm~83mm*83.5mm~163mm,负极极片压实密度为1.0g/cm3~1.5g/cm3,模切尺寸为55.5mm~85mm*85.5mm~165mm,电池容量为0.1-10Ah;所述预钠负极极片是将负极极片在二苯甲酮-钠溶液中浸泡,后清洗,真空条件下干燥获得。
2.根据权利要求1所述的安时级别钠离子软包电池,其特征在于,所述O3层状氧化物正极材料的制备方法为:将碳酸钠、氧化镍、氧化锌、三氧化二铁、二氧化锰及二氧化钛按1:0.3:0.1:0.1:0.3:0.2摩尔计量比例粉碎混合,在空气中煅烧,煅烧温度为800-1100℃,升温速率为1~5℃/min,煅烧时间为12-20小时。
3.根据权利要求2所述的安时级别钠离子软包电池,其特征在于,所述正极极片的制备方法为将O3层状氧化物正极材料、Super-p、PVDF按照93:3:4的质量比混合,并双面涂布到铝箔上80~100℃真空条件下干燥10~15h,获得正极极片,将正极极片辊压至压实密度为2.6g/cm3~3.0g/cm3,再模切至尺寸53.5mm~83mm*83.5mm~163mm。
4.根据权利要求3所述的安时级别钠离子软包电池,其特征在于,所述预钠负极极片的制备方法为将硬碳负极材料、Super-p、丁苯橡胶、羧甲基纤维素按照93:3:2:2的质量混合后双面涂布到铝箔上,70~90℃真空条件下干燥10~15h,获得负极极片,将负极极片辊压至压实密度为1.0g/cm3~1.5g/cm3,再模切至尺寸55.5mm~85mm*85.5mm~165mm,再将负极极片在二苯甲酮-钠溶液中浸泡2~4h,后使用四氢呋喃溶液清洗,70~90℃真空条件下干燥8~12h,获得预钠负极极片。
5.根据权利要求4所述的安时级别钠离子软包电池,其特征在于,二苯甲酮-钠溶液的浓度为0.001-2mol/L。
6.根据权利要求5所述的安时级别钠离子软包电池,其特征在于,所述电解液的浓度为1mol/L,溶质为六氟磷酸钠,溶剂为碳酸甲乙酯、碳酸乙烯酯和碳酸二甲酯以1~2:1~3:1~5体积比混合的混合液。
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