CN111600021A - 硬碳负极材料在钠离子电池上的应用方法 - Google Patents
硬碳负极材料在钠离子电池上的应用方法 Download PDFInfo
- Publication number
- CN111600021A CN111600021A CN202010289904.6A CN202010289904A CN111600021A CN 111600021 A CN111600021 A CN 111600021A CN 202010289904 A CN202010289904 A CN 202010289904A CN 111600021 A CN111600021 A CN 111600021A
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- dgm
- napf
- sodium
- slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 47
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 42
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000007773 negative electrode material Substances 0.000 title claims description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 40
- 229910019398 NaPF6 Inorganic materials 0.000 claims abstract description 18
- 239000010406 cathode material Substances 0.000 claims abstract description 7
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 16
- 239000003575 carbonaceous material Substances 0.000 claims description 14
- 239000006258 conductive agent Substances 0.000 claims description 13
- 239000011149 active material Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical group CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000000661 sodium alginate Substances 0.000 claims description 7
- 235000010413 sodium alginate Nutrition 0.000 claims description 7
- 229940005550 sodium alginate Drugs 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002174 Styrene-butadiene Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910019463 NaV2 Inorganic materials 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000011115 styrene butadiene Substances 0.000 claims description 2
- -1 dimethyl Ether Diol Chemical class 0.000 claims 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 1
- 230000010287 polarization Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 7
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 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 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009459 flexible packaging Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
Classifications
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
本发明涉及硬碳负极材料在钠离子电池上的应用方法,本发明选用商业化硬碳作为钠离子电池的负极材料,NaPF6‑DGM为电解液,Celgard 2325为隔膜,组成的钠离子电池,在电化学性质上具有更小的极化电压和优异的循环倍率性能,同时具有高首效和高库伦效率,兼顾高容量和长寿命,在1A g‑1的电流密度下,循环3500圈,仍然具有224.4mAh g‑1的容量。
Description
技术领域:
本发明提供硬碳负极材料在钠离子电池上的应用方法,属于钠离子电池技术领域。
背景技术:
锂离子电池(LIBs)作为一种新型储能装备已经受到广泛关注(Adv.Mater.2018,30,1800561)。但是随着人们对大型储能装备的需求,锂资源含量的匮乏以及昂贵的价格限制了锂离子电池在大型储能设备中的发展。相对而言,钠离子电池(NIBs)虽然能量密度较低,但在自然界中的含量丰富,与锂的化学性能类似,钠离子电池与锂离子电池的组成、原理相似,可以用铝箔作为集流体,降低了组装成本,越来越受到科研工作者的青睐。但是由于钠离子半径比锂离子半径大,使得钠离子在循环过程中,发生大的体积膨胀效应,从而导致容量的衰减。因此寻找高容量、长循环寿命、优异倍率性能的钠离子负极材料仍然是目前面临的一个挑战(Chem.Soc.Rev.2017,46,3529)。
相对于合金机制的Sb和Sn的负极材料(Adv.Mater.2017,29,1700622),和转化机制的过渡金属氧化物和硫化物(Adv.Funct.Mater.2018,28,1804458),脱嵌机制的材料是最具商业应用潜力的材料(锂离子电池已经给了我们证明),但是已经商业化的锂电负极石墨材料,在钠离子电池中表现出的性能不优异,因为,石墨的层间距并不适合离子半径较大的钠离子进行脱嵌,相对而言,硬碳材料具有无序的结构,更有利于钠离子的吸附和脱嵌(Adv.Energy Mater.2017,7,1602898)。
目前,人们对于硬碳材料的研究分为以下几类:第一,运用不同的原料合成结构不同的硬碳材料,比如纳米结构、空心结构、二维结构等等(J.Alloys Compd.2017,701,870),虽然这些材料表现出好的电化学性能,但是没有商业应用价值。生产中需要的是微米级的材料,具有小的比表面积和高的振实密度,从而表现出高的体积比容量。第二,是对硬碳材料反应机制的探究,综合众多研究,大部分人认为硬碳材料在酯类电解液属于吸附-嵌入机理(Adv.Energy Mater.2017,7,1700403)。并通过各种原位/离位表征手段给出了证明。第三,探究不同电解液以及添加剂对电化学性能的影响(Energy Storage Mater.2019,16,146)。
现有对硬碳材料的研究大都是利用实验室合成的硬碳,对商业化硬碳的利用以及研究很少,同时将硬碳材料用于电池中都忽视了界面膜的形成以及对电化学性能的影响,得到的电池电化学性能都不高。
发明内容:
针对现有技术的不足,本发明提供硬碳负极材料在钠离子电池上的应用方法。
本发明选用商业化硬碳作为钠离子电池的负极材料,NaPF6-DGM为电解液,Celgard 2325为隔膜,组成钠离子电池,通过原位/离位手段对其在该条件下的电化学反应机制、SEI膜的形成机理和成分、以及电解液浓度对其电化学性质的影响进行验证,证明了,在本发明的应用条件下组成的钠离子电池在电化学性质上是具有更小的极化电压和优异的循环倍率性能,具有高首效和高库伦效率,兼顾高容量和长寿命,循环3500圈,仍然具有224.4mAh g-1的容量。
术语说明:
硬碳:是指难以被石墨化的碳,通过高分子聚合物的热分解得到的碳。
商业化硬碳:市场在售硬碳。
为达到以上目的,本发明是通过如下技术方案实现的:
硬碳负极材料在钠离子电池上的应用方法,该应用方法包括:选用商业化硬碳为负极材料,硬碳尺寸为2-10um,比表面积为3-4m2/g,密度为1-2g/cc;将负极材料与导电剂、粘结剂负载在集流体上制得负极片,NaPF6-DGM溶液为电解液,Celgard 2325膜为隔膜,与正极片组成钠离子电池。
根据本发明优选的,所述的NaPF6-DGM溶液为NaPF6溶于二乙二醇二甲醚(DGM)的混合液,二乙二醇二甲醚(DGM)中NaPF6的浓度为0.5-2.5mol/L。
进一步优选的,二乙二醇二甲醚(DGM)中NaPF6的浓度为1mol/L。
根据本发明优选的,隔膜的厚度为20-30um。
根据本发明优选的,负极片的导电剂为乙炔黑,粘结剂为海藻酸钠SA和/或丁苯乳胶SBR,溶剂为水,集流体为铜箔,负极材料、导电剂、粘结剂的质量比为8:1:1。
根据本发明优选的,负极片是按如下方法制备得到:将负极材料、导电剂、粘结剂按质量比8:1:1的比例混合后再加入水,球磨成浆料后涂覆于集流体上,涂覆后于60℃下真空干燥,干燥后滚压,切割成极片,单位面积上硬碳材料的质量为1.5~2.0mg cm-2。
根据本发明优选的,正极片是按如下方法制备得到的:将活性材料、导电剂、粘结剂按质量比8:1:1的比例混合后,加入氮甲基吡咯烷酮(NMP),球磨成浆料后涂覆于铝箔上,涂覆后于80℃下真空干燥,干燥后滚压,切割成极片,单位面积上活性材料的质量为4.0-5.0mgcm-2。
根据本发明优选的,正极导电剂为乙炔黑和/或KS-6,粘结剂为聚偏氟乙烯(PVDF5130)。
根据本发明优选的,当组成钠离子半电池时,正极片上的活性材料为Na片,当组成钠离子全电池时,正极片上的活性材料为NaV2(PO4)3/C,NaV2(PO4)3/C尺寸为5-10um。
本发明的钠离子电池具有以下几个显著的特点:
1、本发明的应用方法采用NaPF6-DGM溶液为电解液,NaPF6相比于NaClO4更加安全,NaClO4在高温下分解容易产生氧气,在密闭的环境中容易爆炸。DGM相比于碳酸乙烯酯/碳酸丙烯酯(EC/DEC)粘度更低,更加有利于电荷的传输,表现在电化学性质上是具有更小的极化电压和优异的倍率性能。隔膜为Celgard2325,相比于Whatman GF/F玻璃纤维膜更加坚韧,阻碍锂枝晶的穿过,使电池更加安全并具有更长的寿命。而且具有更好的柔性,更适合商业化的软包电池。
2、本发明的应用方法负极硬碳材料在醚类电解液中具有和酯类电解液相同的反应机制。通过原位XRD表征得出同样为吸附/嵌入机制,说明本发明采用的电解液并没有改变材料的反应机制。
3、本发明的应用方法硬碳材料以及电解液不会使循环过程中SEI膜分解与重新生成,而是更加坚硬,通过离位核磁技术验证,在首次充放电时,本发明的电解液只有溶质NaPF6发生了分解,而溶剂DGM并没有生变化,不同于酯类电解液中,溶质和溶剂都发生了变化,说明本发明的电解液中SEI膜的成分只有无机物,更加坚硬,不会在循环过程中分解与重新生成,与钠电池具有高首效和高库伦效率是完全符合对应。
4、本发明的应用方法钠离子电池的SEI膜的厚度可以通过调节电解液的浓度进行控制,电解液的溶度还会影响嵌钠个数,本发明采用1M的NaPF6-DGM的电解液浓度兼具高容量和长寿命;在1Ag-1的电流密度下,循环3500圈,仍然具有224.4mAh g-1的容量。
5、本发明选用商业化硬碳作为钠离子电池的负极材料,NaPF6-DGM为电解液,Celgard 2325为隔膜,组成的钠离子电池,在电化学性质上具有更小的极化电压和优异的循环倍率性能,同时具有高首效和高库伦效率,兼顾高容量和长寿命,在1Ag-1的电流密度下,循环3500圈,仍然具有224.4mAh g-1的容量。
附图说明:
图1是本发明实验例1在不同电解液中的首圈库伦效率对比图;a为NaClO4-EC/DEC电解液,b为NaClO4-DGM电解液,c为NaPF6-EC/DEC电解液,d为NaPF6-DGM电解液。
图2是本发明实验例1在NaPF6-DGM电解液中的电化学反应机制充放电曲线和原位XRD衍射花样图;a为充放电曲线,b为原位XRD衍射花样图。
图3是本发明实验例2在NaPF6-DGM电解液中不同电位下的XPS能谱图和离位核磁1H谱图,a为F1s的XPS能谱图,b为离位核磁1H谱图。
图4是本发明实验例2在不同浓度NaPF6-DGM电解液中SEI膜的扫描电镜照片;a为NaPF6的浓度为0.1mol/L的电解液,b为NaPF6的浓度为0.5mol/L的电解液,c为NaPF6的浓度为1.0mol/L的电解液。
图5是本发明实施例1实施例1NaPF6-DGM为电解液,Celgard 2325为隔膜,组成的钠离子电池的长循环性能图。
具体实施方式:
下面将结合附图和实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例中的商业化硬碳,深圳市贝特瑞新能源材料股份有限公司有售。
Celgard 2325膜隔膜,美国celgard隔膜有限公司有售。
实施例1
硬碳负极材料在钠离子电池上的应用方法,该应用方法包括:
(1)负极片制备:将硬碳材料、乙炔黑、粘结剂海藻酸钠(SA)和SBR按质量比8:1:1的比例混合后再加入水,球磨成浆料后涂覆于铜箔上,涂覆后于60℃下真空干燥,干燥后滚压,切割成负极片,单位面积上活性材料的质量为1.5-2.0mg cm-2。
(2)正极片制备:将活性材料、导电剂、粘结剂按质量比8:1:1的比例混合后再加入氮甲基吡咯烷酮(NMP),球磨成浆料后涂覆于铝箔上,涂覆后于80℃下真空干燥,干燥后滚压,切割成极片,单位面积上活性材料的质量为4.0-5.0mg cm-2。
(3)电池组装:包括正极片(Na片以及NaV2(PO4)3/C正极片)、负极片、Celgard 2325隔膜、NaPF6-DGM(NaPF6的浓度为1mol/L)电解液及外壳(型号2032),组装成钠离子半电池或钠离子全电池,电池的组装在手套箱中进行。
对比例1
硬碳负极材料在钠离子电池上的应用方法,同实施例1,不同之处在于,电解液为NaClO4-EC/DEC(NaClO4浓度为1.0mol/L)。
对比例2
硬碳负极材料在钠离子电池上的应用方法,同实施例1,不同之处在于,电解液为NaClO4-DGM(NaClO4浓度为1.0mol/L)。
对比例3
硬碳负极材料在钠离子电池上的应用方法,同实施例1,不同之处在于,电解液为NaPF6-EC/DEC(NaPF6浓度为1.0mol/L)。
实验例1
电化学性能及机理测试
对实施例1以及对比例1-3进行首圈库伦效率测试,从首圈库伦效率可以看出,硬碳材料在NaPF6-DGM电解液中的首效要高于在NaClO4-EC/DEC电解液、NaClO4-DGM电解液和NaPF6-EC/DEC电解液。
图2是本发明实验例1在NaPF6-DGM电解液中的电化学反应机制充放电曲线和原位XRD衍射花样图;a为充放电曲线,b为原位XRD衍射花样图,从图中可以看出,在放电过程中,没有衍射峰的变化,说明只是发生了钠离子的吸附,随着电位的逐渐降低,有新峰NaxC的形成,说明硬碳材料发生了钠离子的嵌入,在充电过程中,NaxC的峰没有完全消失,说明钠离子没有完全脱出,这也是造成首效低的一个原因。
实验例2
SEI膜的形成机理与控制
从离位核磁谱中可以看出,图3a是放电过程中F1s能谱的变化,说明在OCV下NaPF6与水反应产生了NaF,当放电到0.01V时,NaPF6分解产生了NaxPFyOz。图3b为放电过程中1H谱的变化,可以看出在整个放电过程中,DGM都没有发生变化,同时和图1中表现出高的首圈库伦效率是对应的,我们又发现,通过调节电解液的浓度,可以控制SEI膜的厚度,如图4所示,随着电解液浓度的增大,SEI膜也是越来越厚的。
实验例3
电池性能测试
对实施例1NaPF6-DGM为电解液,Celgard 2325为隔膜,钠片为对电极,进行了钠离子电池的长循环测试,测试结果如图5所示,在1A g-1的电流密度下,循环3500圈,还有224.4mAh g-1的容量。这对于其他对比电解液来说,是无法达到的性能。
对比例4
同实施例1所述的硬碳负极材料在钠离子电池上的应用方法,不同之处在于:
步骤(1)负极片制备:粘结剂为羟甲基纤维素钠(CMC)。
改变粘结剂的种类,发现,循环性能远没有海藻酸钠(SA)和SBR复合的好。
对比例5
同实施例1所述的硬碳负极材料在钠离子电池上的应用方法,不同之处在于:
隔膜材料为Whatman GF/F玻璃纤维素膜。
改变隔膜的种类,发现在循环过程中会发生无限充电现象。电压达不到设定的高度。
Claims (9)
1.硬碳负极材料在钠离子电池上的应用方法,该应用方法包括:选用商业化硬碳为负极材料,硬碳尺寸为2-10um,比表面积为3-4m2/g,密度为1-2g/cc;将负极材料与导电剂、粘结剂负载在集流体上制得负极片,NaPF6-DGM溶液为电解液,Celgard 2325膜为隔膜,与正极片组成钠离子电池。
2.根据权利要求1所述的应用方法,其特征在于,所述的NaPF6-DGM溶液为NaPF6溶于二乙二醇二甲醚(DGM)的混合液,二乙二醇二甲醚(DGM)中NaPF6的浓度为0.5-2.5mol/L。
3.根据权利要求2所述的应用方法,其特征在于,二乙二醇二甲醚(DGM)中NaPF6的浓度为1mol/L。
4.根据权利要求1所述的应用方法,其特征在于,隔膜的厚度为20-30um。
5.根据权利要求1所述的应用方法,其特征在于,负极片的导电剂为乙炔黑,粘结剂为海藻酸钠SA和/或丁苯乳胶SBR,溶剂为水,集流体为铜箔,负极材料、导电剂、粘结剂的质量比为8:1:1。
6.根据权利要求1所述的应用方法,其特征在于,负极片是按如下方法制备得到:将负极材料、导电剂、粘结剂按质量比8:1:1的比例混合后再加入水,球磨成浆料后涂覆于集流体上,涂覆后于60℃下真空干燥,干燥后滚压,切割成极片,单位面积上硬碳材料的质量为1.5~2.0mg cm-2。
7.根据权利要求1所述的应用方法,其特征在于,正极片是按如下方法制备得到的:将活性材料、导电剂、粘结剂按质量比8:1:1的比例混合后,加入氮甲基吡咯烷酮(NMP),球磨成浆料后涂覆于铝箔上,涂覆后于80℃下真空干燥,干燥后滚压,切割成极片,单位面积上活性材料的质量为4.0-5.0mg cm-2。
8.根据权利要求7所述的应用方法,其特征在于,正极导电剂为乙炔黑和/或KS-6,粘结剂为聚偏氟乙烯(PVDF5130)。
9.根据权利要求1所述的应用方法,其特征在于,当组成钠离子半电池时,正极片上的活性材料为Na片,当组成钠离子全电池时,正极片上的活性材料为NaV2(PO4)3/C,NaV2(PO4)3/C尺寸为5-10um。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010289904.6A CN111600021A (zh) | 2020-04-14 | 2020-04-14 | 硬碳负极材料在钠离子电池上的应用方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010289904.6A CN111600021A (zh) | 2020-04-14 | 2020-04-14 | 硬碳负极材料在钠离子电池上的应用方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111600021A true CN111600021A (zh) | 2020-08-28 |
Family
ID=72187503
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010289904.6A Pending CN111600021A (zh) | 2020-04-14 | 2020-04-14 | 硬碳负极材料在钠离子电池上的应用方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111600021A (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113381075A (zh) * | 2021-06-09 | 2021-09-10 | 中南大学 | 一种适配于硬碳负极的钠离子电池电解液及其制备和使用方法 |
CN113540398A (zh) * | 2020-04-17 | 2021-10-22 | 北京卫国创芯科技有限公司 | 一种高能量密度锂电池负极及其制备方法 |
CN114725378A (zh) * | 2022-04-22 | 2022-07-08 | 湖南钠方新能源科技有限责任公司 | 一种负极浆料及其制备方法、负极片和二次电池 |
CN114975869A (zh) * | 2022-06-06 | 2022-08-30 | 榆林学院 | 一种扣式钠离子电池及其制备方法 |
CN115010111A (zh) * | 2022-07-22 | 2022-09-06 | 东莞市创明电池技术有限公司 | 一种自支撑钠离子电池负极碳材料及其制备方法和应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105140468A (zh) * | 2015-06-26 | 2015-12-09 | 武汉大学 | 一种钠离子电池正极材料Na3V2(PO4)3/C的制备方法 |
CN107871903A (zh) * | 2017-05-15 | 2018-04-03 | 中国科学院金属研究所 | 一种电容负极/嵌入正极型水系钠离子电容电池 |
WO2019116044A1 (en) * | 2017-12-13 | 2019-06-20 | Faradion Limited | Non-aqueous electrolyte compositions |
-
2020
- 2020-04-14 CN CN202010289904.6A patent/CN111600021A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105140468A (zh) * | 2015-06-26 | 2015-12-09 | 武汉大学 | 一种钠离子电池正极材料Na3V2(PO4)3/C的制备方法 |
CN107871903A (zh) * | 2017-05-15 | 2018-04-03 | 中国科学院金属研究所 | 一种电容负极/嵌入正极型水系钠离子电容电池 |
WO2019116044A1 (en) * | 2017-12-13 | 2019-06-20 | Faradion Limited | Non-aqueous electrolyte compositions |
Non-Patent Citations (1)
Title |
---|
CHENXIAO CHU等: "Uniform nucleation of sodium in 3D carbon nanotube framework via oxygen doping for long-life and efficient Na metal anodes", 《ENERGY STORAGE MATERIALS》 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113540398A (zh) * | 2020-04-17 | 2021-10-22 | 北京卫国创芯科技有限公司 | 一种高能量密度锂电池负极及其制备方法 |
CN113381075A (zh) * | 2021-06-09 | 2021-09-10 | 中南大学 | 一种适配于硬碳负极的钠离子电池电解液及其制备和使用方法 |
CN114725378A (zh) * | 2022-04-22 | 2022-07-08 | 湖南钠方新能源科技有限责任公司 | 一种负极浆料及其制备方法、负极片和二次电池 |
CN114975869A (zh) * | 2022-06-06 | 2022-08-30 | 榆林学院 | 一种扣式钠离子电池及其制备方法 |
CN114975869B (zh) * | 2022-06-06 | 2024-03-08 | 榆林学院 | 一种扣式钠离子电池及其制备方法 |
CN115010111A (zh) * | 2022-07-22 | 2022-09-06 | 东莞市创明电池技术有限公司 | 一种自支撑钠离子电池负极碳材料及其制备方法和应用 |
CN115010111B (zh) * | 2022-07-22 | 2023-09-01 | 东莞市创明电池技术有限公司 | 一种自支撑钠离子电池负极碳材料及其制备方法和应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10770728B2 (en) | Anode material having porous core-shell structure and method of preparing the same and battery | |
Sharma et al. | Progress and challenges in electrochemical energy storage devices: Fabrication, electrode material, and economic aspects | |
CN112993256B (zh) | 一种共价有机框架材料在锂金属负极保护中的应用 | |
CN111600021A (zh) | 硬碳负极材料在钠离子电池上的应用方法 | |
US20120015256A1 (en) | Sodium ion secondary battery | |
CN108565446B (zh) | 一种多孔氮掺杂碳包覆石墨材料的制备方法 | |
CN103811719B (zh) | 一种锂离子电池硅负极极片及其制备方法和锂离子电池 | |
Xu et al. | Status and prospects of Se x S y cathodes for lithium/sodium storage | |
CN114447333B (zh) | 一种钠离子电池 | |
CN110611084B (zh) | 一种具有长循环寿命和100%库伦效率的锂硫二次电池 | |
CN110635116B (zh) | 锂离子电池负极材料及其制备方法、负极和锂离子电池 | |
CN110611099A (zh) | 一种用于锂硫电池正极材料的3D-ZIF8@zif67制备方法 | |
CN110600731B (zh) | 一种钾离子电池正极材料、钾离子电池及制备方法 | |
CN113903891B (zh) | 一种含准金属态锂的无定形碳基复合负极材料的制备方法和应用 | |
US10763543B2 (en) | Rechargeable aqueous hybrid battery | |
JP2017526145A (ja) | リチウムイオン電池用アノード材料 | |
CN109244417B (zh) | 一种纳米片层状结构锂硫电池复合正极材料的制备方法 | |
EP3244472A1 (en) | Composites comprising hollow microspheres of a vanadium oxide for lithium sulfur cells | |
Fan et al. | Protection of lithium anodes by fibrous silica nanospheres | |
CN115818734A (zh) | 一种碳包覆三元正极材料及其制备方法和应用 | |
CN114751395A (zh) | 一种氮掺杂多孔碳球/s复合材料及其制备方法和在锂硫电池中的应用 | |
CN115395013A (zh) | 一种双离子钠电池正极材料的制备方法 | |
CN110165170B (zh) | 一种锂离子电池用负极材料及其制备方法 | |
CN113161603A (zh) | 一种新型钾离子电池及其制备方法 | |
CN112768768A (zh) | 一种含有碘化胺添加剂的电池电解质及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200828 |