CN117012973B - 一种钠离子电池正极极片及钠离子电池 - Google Patents
一种钠离子电池正极极片及钠离子电池 Download PDFInfo
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- CN117012973B CN117012973B CN202311279007.7A CN202311279007A CN117012973B CN 117012973 B CN117012973 B CN 117012973B CN 202311279007 A CN202311279007 A CN 202311279007A CN 117012973 B CN117012973 B CN 117012973B
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- positive electrode
- ion battery
- sodium ion
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 67
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000654 additive Substances 0.000 claims description 62
- 230000000996 additive effect Effects 0.000 claims description 48
- 239000007774 positive electrode material Substances 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 239000006258 conductive agent Substances 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 20
- 239000002041 carbon nanotube Substances 0.000 claims description 19
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- -1 sodium carboxylate Chemical class 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 8
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
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- 239000007773 negative electrode material Substances 0.000 claims description 4
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- 239000000126 substance Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 150000007942 carboxylates Chemical group 0.000 claims description 3
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- 150000003839 salts Chemical class 0.000 claims description 3
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011737 fluorine Substances 0.000 claims description 2
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- 239000010439 graphite Substances 0.000 claims description 2
- 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 description 2
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- 238000003860 storage Methods 0.000 description 17
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
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- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 4
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
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- VSQQQLOSPVPRAZ-RRKCRQDMSA-N trifluridine Chemical compound C1[C@H](O)[C@@H](CO)O[C@H]1N1C(=O)NC(=O)C(C(F)(F)F)=C1 VSQQQLOSPVPRAZ-RRKCRQDMSA-N 0.000 description 3
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- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明提供一种钠离子电池正极极片及钠离子电池,本发明属于钠离子电池技术领域,所述钠离子电池正极极片包括正极活性材料层和正极集流体,所述正极活性材料层位于集流体一侧或者两侧,所述正极活性材料层包含正极活性材料、导电剂、粘结剂和添加剂A,所述添加剂A结构式如式Ⅰ和式Ⅱ所示,本发明的钠离子电池正极极片能够改善钠离子电池正极加工性能,提升钠离子电池的高温循环和高温存储寿命。
Description
技术领域
本发明属于钠离子电池技术领域,涉及一种钠离子电池正极极片及钠离子电池。
背景技术
锂离子电池因具有能量密度高、寿命长、无记忆效应等特点而广泛应用于移动电子设备、电动汽车、无人机等领域。随着使用锂离子电池供电的产品的不断发展和,人们对锂离子电池的能量密度、寿命和快充性能等提出了更高的需求。
然而,锂在地球上的储量有限,成本高居不下,会制约锂电池长期应用。而钠离子电池中的主元素钠在地球上储量丰富,其原料之一碳酸钠价格低廉,很有希望在不久的将来替代锂离子电池。钠离子的电池的正极材料比较有前景的是层状氧化物材料,但是层状氧化物碱性很高,不仅会导致正极浆料加工过程中的凝胶问题,还会加剧正极材料的分解和电解液组份的分解和失效,此外层状氧化物在高温高电压下容易发生相变,产生颗粒破碎、释氧和金属离子溶出,会加剧电解液以及正负极界面的副反应,最终会导致钠离子电池加工性能和高温循环和存储寿命的恶化。
发明内容
针对现有技术的不足,本发明的目的在于提供一种钠离子电池正极极片及钠离子电池。本发明的钠离子电池正极极片能够改善钠离子电池正极加工性能、高温循环和高温存储寿命。
为达此目的,本发明采用以下技术方案:
一方面,本发明提供一种钠离子电池正极极片,所述钠离子电池正极极片包括正极活性材料层和正极集流体,所述正极活性材料层位于集流体一侧或者两侧,所述正极活性材料层包含正极活性材料、导电剂、粘结剂和添加剂A,所述添加剂A结构式如下式Ⅰ或式Ⅱ所示,
;
其中R1、R2、R4、R5为氢原子或碳原子数为1~3的烷基或羧基或碳原子数为1~3的羧酸酯基或羧酸钠,x和y独立地为0或1,R3和R6为氢原子或羟基或含羟基的碳原子数为1~3的亚烷基或碳原子数为1~3的羧基或碳原子数为1~3的羧酸钠。
在本发明中,所述碳原子数1~3指的是碳原子数可以为1、2或3。
优选地,所述添加剂A选自如下式Ⅰ1、Ⅰ2、式Ⅱ1和式Ⅱ2中的至少一种:
其中式Ⅰ1采用现有的尿苷环磷酸(PubChem CID132072335)通过低浓度氢氧化钠酸碱中和反应获得,上述尿苷环磷酸盐制备可参见JP1974117491A或Jozsef Beres等,"Synthesis and antitumor and antiviral properties of 5-halo- and 5-(trifluoromethyl)-2'-deoxyuridine 3',5'-cyclic monophosphates and neutraltriesters",《Journal of Medicinal Chemistry》,第29卷 第7期,第1243–1249页,1986年7月1日。
式Ⅰ2采用采购自Sigma-Aldrich的尿苷环氧磷酸酯(CAS:325683-85-0)与低浓度磷酸缩合后用低浓度氢氧化钠中和获得,相关制备方法参见Jozsef Beres等,"Synthesisand antitumor and antiviral properties of 5-halo- and 5-(trifluoromethyl)-2'-deoxyuridine 3',5'-cyclic monophosphates and neutral triesters",《Journal ofMedicinal Chemistry》,第29卷 第7期,第1243–1249页,1986年7月1日。
式Ⅱ1采购自Sigma-Aldrich,CAS:76567-90-3。
式Ⅱ2采用采购自Sigma-Aldrich的乳清苷(CAS:314-50-1)与低浓度磷酸缩合后用低浓度氢氧化钠中和获得,相关制备方法参见Jozsef Beres等,"Synthesis andantitumor and antiviral properties of 5-halo- and 5-(trifluoromethyl)-2'-deoxyuridine 3',5'-cyclic monophosphates and neutral triesters",《Journal ofMedicinal Chemistry》,第29卷 第7期,第1243–1249页,1986年7月1日。
优选地,以正极活性材料层中正极活性材料、导电剂、粘结剂和添加剂A的总重量为100%计,所述添加剂A的含量为0.1%~2%,例如0.1%、0.3%、0.5%、0.8%、1%、1.3%、1.5%、1.8%或2%。
优选地,所述正极活性材料为层状氧化物,其结构式为NaMx1Oy1,M选自铁、铜、镍、钴或锰元素中的一种或至少两种的组合,0.8≤x1≤1.5,1.5≤y1≤2.5,且x和y的取值满足化学式电荷平衡。
优选地,所述正极活性材料为NaFe0.5Mn0.5O2、NaNi0.3Fe0.4Mn0.3O2、NaNi0.33Fe0.34Mn0.33O2、NaNi0.25Fe0.5Mn0.25O2、NaNi0.2Cu0.1Fe0.4Mn0.3O2、NaNi0.25Fe0.4Co0.1Mn0.25O2、NaNi0.5Fe0.4Mn0.4O2.4或NaNi0.4Fe0.2Mn0.3O1.8的任意一种或至少两种的组合。
优选地,以正极活性材料层中正极活性材料、导电剂、粘结剂和添加剂A的总重量为100%计,所述正极活性材料的含量为90%~98%,例如90%、92%、94%、96%或98%。
优选地,所述导电剂包括炭黑、碳纳米管、石墨烯、导电石墨或碳纤维中的任意一种或至少两种的组合。
优选地,以正极活性材料层中正极活性材料、导电剂、粘结剂和添加剂A的总重量为100%计,所述导电剂的含量为0.5%~8%,例如0.5%、0.8%、1%、1.5%、2%、4%、6%或8%。
优选地,所述导电剂包含炭黑和/或碳纳米管。
优选地,所述导电剂为炭黑和碳纳米管,以正极活性材料层中正极活性材料、导电剂、粘结剂和添加剂A的总重量为100%计,所述碳纳米管在正极活性材料层中的含量为0.1~1%,例如0.1%、0.3%、0.5%、0.8%或1%。
优选地,所述正极集流体选自铝箔、含有其它元素掺杂的铝箔或表面含有涂覆层的铝箔。
第二方面,本发明提供了一种钠离子电池,包括如上所述的钠离子电池正极极片、负极极片、隔离膜和电解液。
优选地,所述负极极片中的负极材料包括硬碳和/或软碳。
优选地,所述电解液包含溶剂、电解质盐和添加剂。
优选地,所述电解液中溶剂包含碳酸酯溶剂、氟代碳酸酯溶剂、羧酸酯溶剂、氟代羧酸酯溶剂、醚类溶剂或氟代醚类溶剂中的任意一种或至少两种的组合。
优选地,所述碳酸酯溶剂为碳酸乙烯酯、碳酸丙烯酯、碳酸丁烯酯、碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸甲乙酯或碳酸甲丙酯中的任意一种或至少两种的组合。
优选地,所述氟代碳酸酯溶剂为氟代碳酸乙烯酯、双氟代碳酸乙烯酯、甲基三氟甲基基碳酸酯、甲基三氟乙基碳酸酯或二(2,2,2-三氟乙基)碳酸酯中的任意一种或至少两种的组合。
优选地,所述羧酸酯溶剂为甲酸甲酯、乙酸甲酯、丙酸甲酯、丁酸甲酯、乙酸乙酯、丙酸乙酯、丙酸丙酯或丁酸乙酯中的任意一种或至少两种的组合。
优选地,所述氟代羧酸酯溶剂为氟代乙酸乙酯、三氟乙酸甲酯、三氟乙酸乙酯、三氟乙酸丙酯、二氟乙酸2,2,2-三氟乙基酯、五氟丙酸甲酯或乙酸-2,2-二氟乙酯中的任意一种或至少两种的组合。
优选地,所述醚类溶剂为四氢呋喃、1,3-二氧五环、乙醚、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚或四乙二醇二甲醚中的任意一种或至少两种的组合。
优选地,所述氟代醚类溶剂为双(2,2,2-三氟乙基)醚、1,1,2,2-四氟乙基-2,2,2-三氟乙基醚或1,1,2,2-四氟乙基-2,2,3,3-四氟丙基醚中的任意一种或至少两种的组合。
优选地,所述电解液中添加剂包括碳酸酯类添加剂、腈类添加剂、含硫元素类添加剂、含氟元素添加剂、含硼元素添加剂或含磷元素添加剂中的任意一种或至少两种的组合。
优选地,所述电解液添加剂为碳酸亚乙烯酯、碳酸乙烯亚乙酯、氟代碳酸乙烯酯、丁二腈、己二腈、乙二醇双(丙腈)醚、1,4-二氰基-2-丁烯、1,2,3-三(2-氰氧基)丙烷、1,3,6-己烷三腈、1,3-丙烷磺酸内酯、1,3-丙烯磺酸内酯,亚硫酸乙烯酯、硫酸乙烯酯、氟代硫酸乙烯酯、硫酸丙烯酯、二氟草酸硼酸钠、三(三甲基硅烷)硼酸酯、三(三甲基硅烷)磷酸酯或三(三甲基硅烷)亚磷酸酯中的任意一种或至少两种的组合。
优选地,所述电解质盐选自NaPF6、NaFSI、NaTFSI、NaBF4、NaClO4、NaAsF6或NaSbF6中的任意一种或至少两种的组合。
与现有技术相比,本发明所达到的有益效果:
本发明通过在钠离子电池正极极片中加入添加剂A,添加剂A的环二酰胺官能团上有氮氢基团,其受旁边两个羰基的吸电子基团影响具有酸性,可以和层状氧化物材料中的强碱反应形成酰胺盐和水等物质,此外添加剂A的环二酰胺官能团可以与正极上的强碱发生开环反应生成羧酸钠、酰胺钠、NH3等物质,水和NH3会挥发掉,剩下的羧酸钠和酰胺钠可以作为正极界面膜的组份抑制正极表面的氧化副反应,也可以减少活性钠离子在正极的消耗,层状氧化物中的强碱被中和掉后就会改善正极浆料凝胶的加工问题,也会抑制强碱对电池使用过程中正极材料表面和电解液的破坏。通过计算,添加剂A的HOMO能级(已占有电子的能级最高的轨道)不仅高于碳酸乙烯酯、碳酸甲乙酯等溶剂,也高于1,3-丙烯磺酸内酯、二氟草酸硼酸钠等正极成膜添加剂,可以优先在正极反应形成界面膜。在电池活化和使用过程中,添加剂A上的环二酰胺官能团和环磷酸钠官能团均可以在正极表面通过开环反应生成致密的界面膜,可以抑制正极表面对电解液的氧化分解和活性钠离子的消耗;同时添加剂A上的环醚官能团、酰胺官能团和磷酸根官能团,可以与正极金属元素结合,起到稳定正极的作用,还可以络合从正极溶出的金属离子,抑制其对电解液和负极的破环作用。因此本发明通过在钠离子电池正极极片中加入添加剂A可以改善钠离子电池的加工性能,高温循环和存储性能。
此外,层状氧化物材料颗粒在高温循环过程中由于相变和膨胀收缩产生的应力导致颗粒破碎,部分导电网络就会中断,而此时在正极极片中加入添加剂A的基础上再加入碳纳米管导电剂,碳纳米管属于线性导电剂,就可以在破碎的颗粒之间搭桥,连通导电网络,进一步改善高温循环和存储性能。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
在本发明实施例中,制作正极极片中所用到的添加剂物料如下所示:
添加剂A:A1、A2、A3;
钠离子电池的制备:
(1)正极片制备
本发明实施例1~10均按照下述制备方法依次制备得到正极极片:
正极材料镍铁锰酸钠NaNi0.3Fe0.4Mn0.3O2、粘结剂聚偏氟乙烯、导电剂的质量比固定为96:2:2,其中粘结剂采购自苏威 SOLEF PVDF 5130、导电剂中导电炭黑采购自卡博特LITX300,碳纳米管采购自天奈科技FT7000,而正极材料镍铁锰酸钠和粘结剂聚偏氟乙烯的含量、导电剂的种类和含量,添加剂A的种类与含量如表1所示。
表1:实施例1~10中正极极片的各组分组成和含量
将正极材料镍铁锰酸钠、粘结剂和导电剂、添加剂A、添加剂B按各自的比例要求进行混合,加入N-甲基吡咯烷酮(NMP)后搅拌制成正极浆料,需要预留正极浆料进行粘度测试。
将正极浆料均匀涂覆于铝箔上,涂布后的铝箔在室温晾干后转移至120℃烘箱干燥1h,随后在85℃下烘干进行冷压、切边、裁片、分条后,在100℃真空条件下干燥4h,焊接极耳,制成满足要求的钠离子二次电池的正极片。
本发明对比例1~3均按照下述制备方法依次制备得到正极极片:
本发明对比例1~3正极材料镍铁锰酸钠和粘结剂聚偏氟乙烯的含量、导电剂的种类和含量,添加剂A的种类与含量如表2所示。
表2:对比例1~3中正极极片的各组分组成和含量
本发明对比例正极极片的具体过程与实施例相同,参考实施例正极极片的制备过程进行制备,需要预留正极浆料进行粘度测试。
(2)电解液制备
首先在手套箱中,在溶剂碳酸乙烯酯(EC)、碳酸二甲酯(DMC)和碳酸甲乙酯(EMC)的混合液中缓慢加入六氟磷酸钠,待容器中温度降到室温后再加入1%氟代碳酸乙烯酯(FEC)添加剂。电解液中EC、DMC和EMC的质量比为EC:DMC:EMC=1:1:1,六氟磷酸钠在电解液中的摩尔浓度为1mol/L。
钠离子电池的制备:
将实施例和对比例中得到的电解液分别应用到钠离子电池中进行性能测试,其中钠离子电池采用如下步骤制备获得:
(2)负极片制备
将硬碳、增稠剂羧甲基纤维素钠(CMC)、粘结剂丁苯橡胶乳液(SBR)和导电炭黑按照质量比94:1:2:3溶于溶剂去离子水中混合均匀制成负极浆料;
将负极浆料均匀涂布在集流体铜箔上,随后在85℃下烘干进行冷压、切边、裁片、分条后,在110℃真空条件下干燥4h,焊接极耳,制成满足要求的钠离子二次电池的负极片。
(3)钠离子电池的制备
将上述相应的正极片、负极片及隔离膜(PE膜+3um陶瓷涂层)经过卷绕成裸电芯后装入铝塑膜,然后在90℃下烘烤除水后,注入电解液再封口,经过静置、热冷压、化成、排气、分容等工序后,得到钠离子电池。
将上述获得的正极浆料和钠离子电池进行测试,包括有以下性能测试:
正极浆料粘度测试
在25℃下,将不同组别的正极出货的浆料取出一部分静置24h后,测试浆料的粘度并记录。
钠离子电池45℃高温循环性能测试
在45℃下,将钠离子电池静置30分钟,之后以0.5C倍率恒流充电至4.05V,然后在4.05V下恒压充电至0.05C,并静置5分钟,之后以0.5C倍率恒流放电至2.0V,此为一个充放电循环过程,得到的放电容量为钠离子电池的首次放电容量C1;之后进行300次充放电循环过程,记录第300此循环的放电容量为C300。
钠离子电池300次循环后的容量保持率(%)=C300/C1。
(3)钠离子电池60℃高温存储测试
首先在25℃将钠离子电池静置30分钟;以0.5C的恒定电流充电至4.05V,进一步以4.05V恒定电压充电至电流为0.05C;然后以0.5C的恒定电流对钠离子电池放电2.0V,此时的放电容量记为C0s;再以0.5C的恒定电流充电至4.05V,进一步以4.05V恒定电压充电至电流为0.05C。之后将钠离子电池置于60℃下存储7天,待存储结束后以0.5C的恒定电流对钠离子电池放电2.0V;再以0.5C的恒定电流对钠离子二次电池充电至4.05V,进一步以4.05V恒定电压充电至电流为0.05C;然后以0.5C的恒定电流对钠离子二次电池放电至2.0V,此时的放电容量记为C7s。之后每隔7天重复上述的操作至70天,记录70天后的放电容量为C70s,此外所有组别钠离子电池测试完成后,拆解电芯,取出负极极片,将负极活性材料层刮下,用强酸消解,过滤后配成溶液,对获得的溶液采用ICP测试其中铁、镍、锰的含量并记录,将ICP测试获得的负极活性材料中铁、镍、锰的含量加和即为负极金属离子沉积量之和。
钠离子存储70天后的存储容量恢复率(%)=C70S/C0S;
本发明实施例和对比例的钠离子电池的性能测试数据参见表3。
表3:钠离子电池的测试结果
从表3中对比例1~2、及实施例1~3可以看出,相比于不加添加剂A的正极极片,在钠离子电池正极极片中加入添加剂A后,正极浆料的24h静置后粘度、45℃循环、60℃存储容量恢复和负极金属离子沉积均得到明显改善。其中添加剂A能中和正极中的残碱,明显改善24h静置后的粘度和凝胶现象,从而改善正极极片的加工性能;添加剂A能络合正极溶出到表面的过度金属离子,明显减少后者在负极的沉积,添加剂A可以在正极通过开环反应形成致密的界面膜,可以改善45℃循环和60℃存储容量。随着添加剂A含量的增加,钠离子电池的各项性能均持续改善;但是当添加剂A过量时,添加剂A有一定的酸性,会导致正极部分浆料团聚,浆料粘度反而可能上升,同时酸性成分也会破坏正极表面和导致电解液组份的分解,从而恶化45℃循环和60℃存储性能,因此添加剂A的含量必须控制在一定的范围。从表3中实施例2、实施例4~5可以看出,使用不同的添加剂A种类和含量可以得到不同的效果。
从表3中对比例3和实施例5~8可以看出,在正极极片加入添加剂A的基础上,随着碳纳米管的含量增加,45℃循环、60℃存储容量恢复和负极金属离子沉积均有一定的改善;但是正极浆料的24h静置后粘度是逐次恶化的,这主要是因为碳纳米管是很难分散的添加剂,在正极浆料容易团聚,所以粘度会上升。此外当碳纳米管过量时,45℃循环和60℃存储反而会恶化,推测一方面是由于碳纳米管明显提升时炭黑的含量会相应下降,炭黑在正极颗粒之间是点接触形成的导电网络更多,炭黑含量太低意味着整个正极片导电网络不足,不利于钠离子的传输,此外碳纳米管含量增加导致其在局部区域团聚,碳纳米管多的区域导电性强电流密度大,产生局部区域过充过放,从而恶化循环和存储性能。从表3中实施例7、实施例9~10可以看出,不同的添加剂A种类、含量与不同含量的碳纳米管组合,可以得到不同的改善效果。
综上所述,本发明通过在钠离子电池正极极片中组合使用添加剂A,可以显著改善正极极片的加工性能,同时可以提高钠离子电池的循环寿命和高温存储容量恢复,以及抑制高温存储过程负极中金属离子的沉积;在正极极片中组合使用添加剂A的基础上,再加入碳纳米管可以进一步改善钠离子电池的循环和高温存储性能。
申请人声明,本发明通过上述实施例来说明本发明的钠离子电池正极极片及钠离子电池,但本发明并不局限于上述实施例,即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (10)
1.一种钠离子电池正极极片,其特征在于,所述钠离子电池正极极片包括正极活性材料层和正极集流体,所述正极活性材料层位于集流体一侧或者两侧,所述正极活性材料层包含正极活性材料、导电剂、粘结剂和添加剂A,所述添加剂A结构式如下式Ⅰ或式Ⅱ所示,
;
其中R1、R2、R4、R5为氢原子或碳原子数为1~3的烷基或羧基或碳原子数为1~3的羧酸酯基或羧酸钠,x和y独立地为0或1,R3和R6为氢原子或羟基或含羟基的碳原子数为1~3的亚烷基或碳原子数为1~3的羧基或碳原子数为1~3的羧酸钠。
2.根据权利要求1所述的钠离子电池正极极片,其特征在于,所述添加剂A选自如下式Ⅰ1、Ⅰ2、式Ⅱ1和式Ⅱ2中的任意一种:
。
3.根据权利要求1所述的钠离子电池正极极片,其特征在于,以正极活性材料层中正极活性材料、导电剂、粘结剂和添加剂A的总重量为100%计算,所述添加剂A的含量为0.1%~2%。
4.根据权利要求1所述的钠离子电池正极极片,其特征在于,所述正极活性材料为层状氧化物,其结构式为NaMx1Oy1,M选自铁、铜、镍、钴或锰元素中的一种或至少两种的组合,0.8≤x1≤1.5,1.5≤y1≤2.5,且x1和y1的取值满足化学式电荷平衡。
5.根据权利要求1所述的钠离子电池正极极片,其特征在于,所述正极活性材料为NaFe0.5Mn0.5O2、NaNi0.3Fe0.4Mn0.3O2、NaNi0.33Fe0.34Mn0.33O2、NaNi0.25Fe0.5Mn0.25O2、NaNi0.2Cu0.1Fe0.4Mn0.3O2、NaNi0.25Fe0.4Co0.1Mn0.25O2、NaNi0.5Fe0.4Mn0.4O2.4或NaNi0.4Fe0.2Mn0.3O1.8的任意一种或至少两种的组合。
6.根据权利要求1所述的钠离子电池正极极片,其特征在于,所述导电剂包含炭黑、碳纳米管、石墨烯、导电石墨、碳纤维中的任意一种或多种。
7.根据权利要求1所述的钠离子电池正极极片,其特征在于,所述导电剂为炭黑和碳纳米管,以正极活性材料层中正极活性材料、导电剂、粘结剂和添加剂A的总重量为100%计,所述碳纳米管在正极活性材料层中的含量为0.1~1%。
8.根据权利要求1所述的钠离子电池正极极片,其特征在于,所述正极集流体选自铝箔、含有其它元素掺杂的铝箔或表面含有涂覆层的铝箔中的一种。
9.一种钠离子电池,其特征在于,所述钠离子电池包括如权利要求1-8中任一项所述的钠离子电池正极极片、负极极片、隔离膜和电解液。
10.根据权利要求9所述的钠离子电池,其特征在于,所述负极极片中的负极材料包括硬碳和/或软碳;
所述电解液包含溶剂、电解质盐和添加剂;
所述电解液中添加剂包括碳酸酯类添加剂、腈类添加剂、含硫元素类添加剂、含氟元素添加剂、含硼元素添加剂或含磷元素添加剂中的任意一种或至少两种的组合。
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