WO2018023322A1 - 一种含复合石墨烯涂层正极片的制备方法 - Google Patents
一种含复合石墨烯涂层正极片的制备方法 Download PDFInfo
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- WO2018023322A1 WO2018023322A1 PCT/CN2016/092655 CN2016092655W WO2018023322A1 WO 2018023322 A1 WO2018023322 A1 WO 2018023322A1 CN 2016092655 W CN2016092655 W CN 2016092655W WO 2018023322 A1 WO2018023322 A1 WO 2018023322A1
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- Prior art keywords
- positive electrode
- electrode sheet
- lithium
- graphene
- lithium ion
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011248 coating agent Substances 0.000 title claims abstract description 8
- 238000000576 coating method Methods 0.000 title claims abstract description 8
- 239000002131 composite material Substances 0.000 title abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011230 binding agent Substances 0.000 claims abstract description 28
- 239000006258 conductive agent Substances 0.000 claims abstract description 28
- 239000002002 slurry Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 21
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 18
- 239000010439 graphite Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000011149 active material Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims abstract 2
- 239000003792 electrolyte Substances 0.000 claims description 13
- 239000011888 foil Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010405 anode material Substances 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 7
- 229910021385 hard carbon Inorganic materials 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 10
- 238000009830 intercalation Methods 0.000 abstract description 3
- 230000002687 intercalation Effects 0.000 abstract description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract 1
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 1
- 239000002033 PVDF binder Substances 0.000 description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 15
- 239000003273 ketjen black Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000003475 lamination Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention belongs to the technical field of lithium ion supercapacitors, and relates to a method for preparing a positive electrode sheet of a lithium ion supercapacitor.
- the battery negative electrode generally uses a carbon material such as graphite
- the positive electrode uses a lithium-containing metal oxide such as lithium cobaltate or lithium manganate.
- the charged negative electrode supplies lithium ions to the positive electrode, and the lithium ion of the positive electrode of the discharge positive electrode returns to the negative electrode, so it is called a "rocking chair type battery".
- This battery is characterized by high safety and high cycle life compared to lithium batteries using metallic lithium.
- Lithium-ion capacitors generally use carbon materials such as graphite and hard carbon for the anode material, and activated carbon materials with double-layer characteristics for the cathode material, and the lithium anode is pre-diffused to the anode material, so that the potential of the anode is greatly reduced, thereby improving Energy Density.
- a lithium ion capacitor is disclosed in the special ljCN200580001498.2.
- the positive current collector and the negative current collector used in the lithium ion capacitor have holes penetrating the front and back surfaces, and the electrode layer is formed by the positive electrode active material and the negative electrode active material respectively. Electrochemical contact is made to the negative electrode, and lithium ions are carried in the negative electrode in advance.
- a pretreatment method for a negative electrode for an electrochemical capacitor is disclosed in the Japanese Patent Publication No. Hei. No. 1,200, 406, 9.6, a lithium layer is formed on a substrate by a vapor phase method or a liquid phase method, and then the lithium layer is transferred to an electrode layer of a negative electrode.
- These pre-excessive methods involve complex processes and require special handling of the raw materials, which makes the manufacturing process difficult.
- the technical problem to be solved by the present invention is to provide a method for preparing a positive electrode sheet for a lithium ion supercapacitor.
- the positive electrode sheet prepared by the method can provide a lithium source in a lithium ion capacitor, thereby eliminating the need for complicated pre-processing of the negative electrode.
- Lithium-intercalation or the addition of lithium wafers to lithium-ion capacitors simplifies the preparation of lithium-ion capacitors The process reduces the cost of the process.
- the preparation method of the lithium ion supercapacitor positive electrode sheet provided by the invention is:
- Step (1) The graphite oxide and Li 2 CO 3 are mixed at a mass ratio of 50-10:1, uniformly mixed, and then placed in a nitrogen-protected muffle furnace at 200-600 ° C for 1-6 h to obtain A graphene material containing an alcohol-based lithium.
- Step (2) The graphene material containing a lithium alcohol, a conductive agent, and a binder are added to the NMP in a mass ratio of 80-90:5-10:5-10, and then mixed into a slurry, and then coated. On the positive electrode sheet containing the active material, after drying, a graphene-coated positive electrode sheet containing an alcohol-based lithium was obtained.
- the step (1) is carried out in a muffle furnace at a reaction temperature of 200-600 ° C, and the reaction time is 1-6 hours;
- the atmosphere in the muffle furnace is nitrogen
- the mass ratio of the graphene material, the conductive agent and the binder containing the lithium alcohol in the step (2) is 80-90:5-10:5-10;
- the present invention provides a lithium ion supercapacitor preparation process as follows:
- the negative electrode sheet, the separator and the positive electrode sheet are formed into a battery cell by lamination according to a preparation process of a usual lithium ion battery, and then an electrolyte is injected into the battery case, and the injected electrolyte is 1 mol/L LiPF 6 DOL-DME solution (DOL and DME volume ratio is 1:1), sealed, to get lithium ion supercapacitor
- the process for preparing a lithium ion supercapacitor using the positive electrode material of the present invention is a general-purpose lithium ion battery preparation Art, greatly simplifying the preparation process of lithium ion supercapacitors.
- the positive electrode sheet coated with the graphene material containing the alcohol lithium prepared by the invention is used as a positive electrode sheet of a lithium ion supercapacitor, and the graphene material coating containing the lithium alcohol provides a lithium source, and the lithium ion is charged for the first time.
- the lithium alcohol is extracted into the graphite negative electrode to lower the negative electrode potential. Therefore, it is not necessary to use a lithium metal plate or a complicated pre-intercalation lithium process in the negative electrode; the same graphene can also serve as a positive active material in the positive electrode, thereby increasing the capacity of the positive electrode. .
- the present invention has the following beneficial effects: (1)
- the positive electrode sheet coated with the graphene material containing lithium alcohol is the positive electrode of the lithium ion super capacitor, so that the negative electrode does not need to be added with a lithium sheet or a complicated pre-lithium process, simplifying The preparation process reduces costs.
- FIG. 1 is a schematic structural view of a positive electrode sheet of a lithium ion supercapacitor of the present invention.
- a 1_ collector a 2-active material positive electrode sheet, and a graphene material-coated positive electrode sheet containing an alcohol-based lithium.
- a ratio of 10:10 was added to the NMP and mixed into a slurry, which was then coated on a positive electrode sheet containing the active material, and dried to obtain a graphene material-coated positive electrode sheet 3 containing an alcohol-based lithium.
- the graphite negative electrode material, the conductive agent Ketjen black, and the binder PVDF are added to the NMP in a mass ratio of 90:5:5 to be mixed into a slurry, and then coated on the negative electrode current collector copper foil foil. Above, after drying, a negative electrode sheet is obtained.
- the negative electrode sheet, the separator and the positive electrode sheet are assembled into a cell according to a preparation process of a usual lithium ion battery, and then an electrolyte is injected into the battery case, and the injected electrolyte is 1 mol/L LiPF 6 DOL-DME solution (DOL and DME volume ratio is 1:1), sealed, to get lithium ion supercapacitor
- the negative electrode sheet, the separator and the positive electrode sheet are formed into a battery cell by lamination according to a preparation process of a usual lithium ion battery, and then an electrolyte is injected into the battery case, and the injected electrolyte is 1 mol/L LiPF 6 .
- DOL-DME solution (DOL and DME volume ratio is 1:1), sealed, to get lithium ion supercapacitor
- the negative electrode sheet, the separator and the positive electrode sheet are assembled into a battery cell by lamination according to a usual preparation process of a lithium ion battery, and then an electrolyte is injected into the battery case, and the injected electrolyte is 1 mol/L LiPF 6 .
- DOL-DME solution (DOL and DME volume ratio is 1:1), sealed, to get lithium ion supercapacitor
- the negative electrode sheet, the separator and the positive electrode sheet are assembled into a cell according to a preparation process of a usual lithium ion battery, and then an electrolyte is injected into the battery case, and the injected electrolyte is 1 mol/L LiPF 6 DOL-DME solution (DOL and DME volume ratio is 1:1), sealed, to get lithium ion supercapacitor
- Example 5 [0052] (1) The graphite oxide and the Li 2 CO 3 are mixed at a mass ratio of 40:1, uniformly mixed, and then placed in a nitrogen-protected muffle furnace at 500 ° C for 4 hours to obtain a graphene containing an alcohol-based lithium. material.
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
一种含复合石墨烯涂层正极片的制备方法,包括以下步骤:步骤(1)将氧化石墨和Li 2CO 3混合,混合均匀后放入气体保护的马弗炉内反应,得到含有醇基锂的石墨烯材料;步骤(2)将含有醇基锂的石墨烯材料、导电剂、粘结剂按照比例加入到NMP中混合成浆料,然后涂覆在含有活性材料正极片上,烘干后得到含有醇基锂的石墨烯涂层正极片。含有醇基锂的石墨烯材料涂层的正极片为锂离子超级电容器的正极使负极不需要再加入锂片或者复杂的预嵌锂工艺,简化了制备工艺,降低了成本。
Description
一种含复合石墨烯涂层正极片的制备方法 技术领域
[0001] 本发明属于锂离子超级电容器技术领域, 涉及一种锂离子超级电容器正极片的 制备方法。
背景技术
[0002] 近年来, 锂离子二次电池得到了很大的发展, 这种电池负极一般使用石墨等炭 素材料, 正极使用钴酸锂、 锰酸锂等含锂金属氧化物。 这种电池组装以后, 充 电吋负极向正极提供锂离子, 而在放电吋正极的锂离子又返回负极, 因此被称 为"摇椅式电池"。 与使用金属锂的锂电池相比, 这种电池具有高安全性和高循环 寿命的特点。
[0003] 但是, 由于正极材料在脱嵌锂的过程中容易发生结构的变形, 因此, 锂离子二 次电池的循环寿命仍受到制约。 因此近年来, 把锂离子二次电池和双层电容器 结合在一起的体系研究成为新的热点。
[0004] 锂离子电容器一般负极材料选用石墨、 硬碳等炭素材料, 正极材料选用双电层 特性的活性炭材料, 通过对负极材料进行锂离子的预惨杂, 使负极电位大幅度 下降, 从而提高能量密度。 专禾 ljCN200580001498.2中公幵了一种锂离子电容器 , 这种锂离子电容器使用的正极集流体和负极集流体均具有贯穿正反面的孔, 分别由正极活性物质和负极活性物质形成电极层, 通过对负极进行电化学接触 , 预先把锂离子承载在负极中。 专禾 ljCN200780024069.6中公幵了一种电化学电 容器用负极的预处理方法, 通过气相法或液相法在基板上形成锂层, 然后将该 锂层转印到负极的电极层。 这些预惨杂的方法涉及到的工艺比较复杂, 且对原 材料需要进行特殊处理, 给制造过程带来一定难度。
技术问题
[0005] 本发明要解决的技术问题是提供一种锂离子超级电容器正极片的制备方法, 该 方法制备的正极片可在锂离子电容器中提供锂源, 从而不需要再对负极进行复 杂的预嵌锂处理或者在锂离子电容器中添加锂片, 简化了锂离子电容器制备的
工艺过程, 降低了其工艺成本。
问题的解决方案
技术解决方案
[0006] 本发明提供的锂离子超级电容器正极片的制备方法为:
[0007] 步骤 (1) 将氧化石墨和 Li 2CO 3按质量比 50-10:1的比例混合, 混合均匀后放入 氮气保护的马弗炉内 200-600°C反应 l-6h, 得到含有醇基锂的石墨烯材料。
[0008] 步骤 (2) 将含有醇基锂的石墨烯材料、 导电剂、 粘结剂按照 80-90:5-10:5-10的 质量比例加入到 NMP中混合成浆料, 然后涂覆在含有活性材料正极片上, 烘干 后得到含有醇基锂的石墨烯涂层正极片。
[0009] 进一步地
[0010] 进一步地 所述步骤 (1) 在马弗炉内的反应温度为 200-600°C, 反应吋间为 1-6 小吋;
[0011] 进一步地 所述步骤 (2) 中马弗炉内的气氛为氮气;
[0012] 进一步地 所述步骤 (2) 中含有醇基锂的石墨烯材料、 导电剂、 粘结剂的质 量比为 80-90:5-10:5-10;
[0013] 本发明提供一种锂离子超级电容器的制备工艺流程如下:
[0014] (1) 将活性炭或者石墨烯正极材料、 导电剂、 粘结剂按照 90:5:5的比例加入到 NMP中混合成浆料, 然后涂覆在正极集流体铝箔上, 烘干后得到正极片。
[0015] (2) 将含有醇基锂的石墨烯材料、 导电剂、 粘结剂按照 80-90:5-10:5-10的质量 比例加入到 NMP中混合成浆料, 然后涂覆在含有活性材料正极片上, 烘干后得 到含有醇基锂的石墨烯材料涂层正极片。
[0016] (3) 将石墨或者硬炭负极材料、 导电剂、 粘结剂按照 90:5:5的比例加入到 NMP 中混合成浆料, 然后涂覆在负极集流体铜箔箔上, 烘干后得到负极片。
[0017] (4) 按照通常锂离子电池的制备工艺将负极片、 隔膜和正极片通过叠层的方 式组成电芯, 然后在电池壳内注入电解液, 注入的电解液为 lmol/L LiPF 6 的 DOL-DME溶液 (DOL和 DME的体积比为 1:1), 封口, 得到锂离子超级电容器
[0018] 采用本发明正极材料制备锂离子超级电容器的工艺为通用的锂离子电池制备工
艺, 大大简化了锂离子超级电容器的制备工艺。
[0019] 本发明制备的含有醇基锂的石墨烯材料涂层的正极片用作锂离子超级电容器正 极片吋, 含有醇基锂的石墨烯材料涂层提供锂源, 在首次充电吋锂离子脱出醇 基锂插入到石墨负极中, 从而拉低负极电位, 因此负极中不需要采用金属锂片 或者复杂的预嵌锂工艺; 同吋石墨烯在正极也可以充当正极活性材料, 提高正 极的容量。
发明的有益效果
有益效果
[0020] 本发明具有如下有益效果: (1) 含有醇基锂的石墨烯材料涂层的正极片为锂 离子超级电容器的正极使负极不需要再加入锂片或者复杂的预嵌锂工艺, 简化 了制备工艺, 降低了成本。
对附图的简要说明
附图说明
[0021] 图 1是本发明锂离子超级电容器正极片结构示意图。
[0022] 图中, 1_集流体, 2_活性材料正极片, 3_含有醇基锂的石墨烯材料涂层正 极片。
本发明的实施方式
[0023] 下面结合附图, 对本发明的较优的实施例作进一步的详细说明:
[0024] 实施例 1
[0025] (1) 将氧化石墨和 Li ^0 3按质量比 50:1的比例混合, 混合均匀后放入氮气保 护的马弗炉内 200°C反应 6h, 得到含有醇基锂的石墨烯材料。
[0026] (2) 将活性炭材料、 导电剂科琴黑、 粘结剂 PVDF按照质量比 90:5:5的比例加 入到 NMP中混合成浆料, 然后涂覆在正极集流体 1铝箔上, 烘干后得到正极片。
[0027] (3) 将含有醇基锂的石墨烯材料、 导电剂科琴黑、 粘结剂 PVDF按照质量比 80
: 10: 10的比例加入到 NMP中混合成浆料, 然后涂覆在含有活性材料正极片上, 烘干后得到含有醇基锂的石墨烯材料涂层正极片 3。
[0028] (4) 将石墨负极材料、 导电剂科琴黑、 粘结剂 PVDF按照质量比 90:5:5的比例 加入到 NMP中混合成浆料, 然后涂覆在负极集流体铜箔箔上, 烘干后得到负极 片。
[0029] (5) 按照通常锂离子电池的制备工艺将负极片、 隔膜和正极片通过叠层的方 式组成电芯, 然后在电池壳内注入电解液, 注入的电解液为 lmol/L LiPF 6 的 DOL-DME溶液 (DOL和 DME的体积比为 1:1), 封口, 得到锂离子超级电容器
[0030]
[0031] 实施例 2
[0032] (1) 将氧化石墨和 Li 2CO 3按质量比 10:1的比例混合, 混合均匀后放入氮气保 护的马弗炉内 600°C反应 lh, 得到含有醇基锂的石墨烯材料。
[0033] (2) 将活性炭材料、 导电剂科琴黑、 粘结剂 PVDF按照质量比 90:5:5的比例加 入到 NMP中混合成浆料, 然后涂覆在正极集流体 1铝箔上, 烘干后得到正极片。
[0034] (3) 将含有醇基锂的石墨烯材料、 导电剂科琴黑、 粘结剂 PVDF按照 90:5:5的 质量比例加入到 NMP中混合成浆料, 然后涂覆在含有活性材料正极片 2上, 烘干 后得到含有醇基锂的石墨烯材料涂层正极片 3。
[0035] (4) 将硬炭负极材料、 导电剂科琴黑、 粘结剂 PVDF按照质量比 90:5:5的比例 加入到 NMP中混合成浆料, 然后涂覆在负极集流体铜箔箔上, 烘干后得到负极 片。
[0036] (5) 按照通常锂离子电池的制备工艺将负极片、 隔膜和正极片通过叠层的方 式组成电芯, 然后在电池壳内注入电解液, 注入的电解液为 lmol/L LiPF 6 的 DOL-DME溶液 (DOL和 DME的体积比为 1:1), 封口, 得到锂离子超级电容器
[0037] 实施例 3
[0038] (1) 将氧化石墨和 Li 2CO 3按质量比 20:1的比例混合, 混合均匀后放入氮气保 护的马弗炉内 300°C反应 5h, 得到含有醇基锂的石墨烯材料。
[0039] (2) 将活性炭材料、 导电剂科琴黑、 粘结剂 PVDF按照质量比 90:5:5的比例加 入到 NMP中混合成浆料, 然后涂覆在正极集流体 1铝箔上, 烘干后得到正极片。
[0040] (3) 将含有醇基锂的石墨烯材料、 导电剂科琴黑、 粘结剂 PVDF按照 85:7:8的 质量比例加入到 NMP中混合成浆料, 然后涂覆在含有活性材料正极片 2上, 烘干 后得到含有醇基锂的石墨烯材料涂层正极片 3。
[0041] (4) 将石墨负极材料、 导电剂科琴黑、 粘结剂 PVDF按照质量比 90:5:5的比例 加入到 NMP中混合成浆料, 然后涂覆在负极集流体铜箔箔上, 烘干后得到负极 片。
[0042] (5) 按照通常锂离子电池的制备工艺将负极片、 隔膜和正极片通过叠层的方 式组成电芯, 然后在电池壳内注入电解液, 注入的电解液为 lmol/L LiPF 6 的 DOL-DME溶液 (DOL和 DME的体积比为 1:1), 封口, 得到锂离子超级电容器
[0043]
[0044] 实施例 4
[0045] (1) 将氧化石墨和 Li ^0 3按质量比 30:1的比例混合, 混合均匀后放入氮气保 护的马弗炉内 400°C反应 2h, 得到含有醇基锂的石墨烯材料。
[0046] (2) 将活性炭材料、 导电剂科琴黑、 粘结剂 PVDF按照质量比 90:5:5的比例加 入到 NMP中混合成浆料, 然后涂覆在正极集流体 1铝箔上, 烘干后得到正极片。
[0047] (3) 将含有醇基锂的石墨烯材料、 导电剂科琴黑、 粘结剂 PVDF按照质量比 82
:9:9的质量比例加入到 NMP中混合成浆料, 然后涂覆在含有活性材料正极片 2上
, 烘干后得到含有醇基锂的石墨烯材料涂层正极片 3。
[0048] (4) 将硬炭负极材料、 导电剂科琴黑、 粘结剂 PVDF按照质量比 90:5:5的比例 加入到 NMP中混合成浆料, 然后涂覆在负极集流体铜箔箔上, 烘干后得到负极 片。
[0049] (5) 按照通常锂离子电池的制备工艺将负极片、 隔膜和正极片通过叠层的方 式组成电芯, 然后在电池壳内注入电解液, 注入的电解液为 lmol/L LiPF 6 的 DOL-DME溶液 (DOL和 DME的体积比为 1:1), 封口, 得到锂离子超级电容器
[0050]
[0051] 实施例 5
[0052] (1) 将氧化石墨和 Li 2CO 3按质量比 40:1的比例混合, 混合均匀后放入氮气保 护的马弗炉内 500°C反应 4h, 得到含有醇基锂的石墨烯材料。
[0053] (2) 将活性炭材料、 导电剂科琴黑、 粘结剂 PVDF按照质量比 90:5:5的比例加 入到 NMP中混合成浆料, 然后涂覆在正极集流体 1铝箔上, 烘干后得到正极片。
[0054] (3) 将含有醇基锂的石墨烯材料、 导电剂科琴黑、 粘结剂 PVDF按照 88:6:6的 质量比例加入到 NMP中混合成浆料, 然后涂覆在含有活性材料正极片 2上, 烘干 后得到含有醇基锂的石墨烯材料涂层正极片 3。
[0055] (4) 将石墨负极材料、 导电剂科琴黑、 粘结剂 PVDF按照质量比 90:5:5的比例 加入到 NMP中混合成浆料, 然后涂覆在负极集流体铜箔箔上, 烘干后得到负极 片。
[0056] (5) 按照通常锂离子电池的制备工艺将负极片、 隔膜和正极片通过叠层的方 式组成电芯, 然后在电池壳内注入电解液, 注入的电解液为 lmol/L LiPF 6 的 DOL-DME溶液 (DOL和 DME的体积比为 1:1), 封口, 得到锂离子超级电容器
[0057] 其效果如表 1所示, 由表 1可知: 本发明制备的锂离子超级电容器能量密度达到 了 44.8-47.1 wh/kg, 达到了常用锂离子超级电容器的能量密度水平。
[0058] 表 1
[] [表 1]
Claims
[权利要求 1] 一种锂离子超级电容器正极片的制备方法, 其特征在于, 包括以下几 个步骤:
步骤 (1) 将氧化石墨和 Li 2C0 3混合, 混合均匀后放入气体保护的马 弗炉内反应, 得到含有醇基锂的石墨烯材料;
步骤 (2) 将含有醇基锂的石墨烯材料、 导电剂、 粘结剂加入到 NMP 中混合成浆料, 然后涂覆在含有活性材料正极片上, 烘干后得到含有 醇基锂的石墨烯涂层正极片。
[权利要求 2] —种锂离子超级电容器正极片的制备方法, 其特征在于, 所述步骤 (
1) 中氧化石墨和 Li 2CO 3按质量比 50-10:1的比例混合。
[权利要求 3] —种锂离子超级电容器正极片的制备方法, 其特征在于, 所述步骤 (
1) 在马弗炉内的反应温度为 200-600°C, 反应吋间为 1-6小吋。
[权利要求 4] 一种锂离子超级电容器正极片的制备方法, 其特征在于, 所述步骤 (
2) 中马弗炉内的气氛为氮气。
[权利要求 5] —种锂离子超级电容器的制备工艺, 其特征在于, 包括以下几个步骤 步骤 A:将活性炭或者石墨烯正极材料、 导电剂、 粘结剂加入到 NMP 中混合成浆料, 然后涂覆在正极集流体铝箔上, 烘干后得到正极片; 步骤 B:将含有醇基锂的石墨烯材料、 导电剂、 粘结剂加入到 NMP中 混合成浆料, 然后涂覆在含有活性材料正极片上, 烘干后得到含有醇 基锂的石墨烯材料涂层正极片;
步骤 C:将石墨或者硬炭负极材料、 导电剂、 粘结剂加入到 NMP中混 合成浆料, 然后涂覆在负极集流体铜箔箔上, 烘干后得到负极片; 步骤 D:按照通常锂离子电池的制备工艺将负极片、 隔膜和正极片通过 叠层的方式组成电芯, 然后在电池壳内注入电解液, 封口, 得到锂离 子超级电容器。
[权利要求 6] 如权利要求 5所述的制备工艺, 其特征在于, 所述步骤 A中, 活性炭 或者石墨烯正极材料、 导电剂、 粘结剂质量比 90:5:5; 所述步骤 C中
, 石墨或者硬炭负极材料、 导电剂、 粘结剂质量比 90:5:5。
[权利要求 7] 如权利要求 5所述的制备工艺, 其特征在于, 所述步骤 B和步骤 (2)
中, 含有醇基锂的石墨烯材料、 导电剂、 粘结剂按照质量比 80-90:5-1 0:5-10。
[权利要求 8] 如权利要求 5所述的制备工艺, 其特征在于, 所述步骤 C中, 所述电 解液为 lmol/L LiPF 6的 DOL-DME溶液, 其中, DOL和 DME的体积 比为 1:1。
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NO20190459A1 (en) * | 2019-04-04 | 2020-10-05 | Ipr Holding As | Method for pre-lithiating a lithium-ion capacitor |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5910382A (en) * | 1996-04-23 | 1999-06-08 | Board Of Regents, University Of Texas Systems | Cathode materials for secondary (rechargeable) lithium batteries |
CN102201275A (zh) * | 2010-03-25 | 2011-09-28 | 海洋王照明科技股份有限公司 | 锂盐-石墨烯复合材料及其制备方法与应用 |
CN102683658A (zh) * | 2012-05-21 | 2012-09-19 | 焦作聚能能源科技有限公司 | 一种锂离子电池用石墨/LiAlO2/石墨烯复合材料及其制备方法 |
CN103022459A (zh) * | 2012-11-27 | 2013-04-03 | 中国科学院大连化学物理研究所 | 一种石墨烯/钛酸锂复合负极材料的制备方法 |
CN103367708A (zh) * | 2012-03-29 | 2013-10-23 | 海洋王照明科技股份有限公司 | 电池正极及其制备方法、电池负极及其制备方法、电容电池 |
US20150044556A1 (en) * | 2013-08-08 | 2015-02-12 | Yanbo Wang | Cathode active material-coated discrete graphene sheets for lithium batteries and process for producing same |
-
2016
- 2016-07-31 WO PCT/CN2016/092655 patent/WO2018023322A1/zh active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5910382A (en) * | 1996-04-23 | 1999-06-08 | Board Of Regents, University Of Texas Systems | Cathode materials for secondary (rechargeable) lithium batteries |
CN102201275A (zh) * | 2010-03-25 | 2011-09-28 | 海洋王照明科技股份有限公司 | 锂盐-石墨烯复合材料及其制备方法与应用 |
CN103367708A (zh) * | 2012-03-29 | 2013-10-23 | 海洋王照明科技股份有限公司 | 电池正极及其制备方法、电池负极及其制备方法、电容电池 |
CN102683658A (zh) * | 2012-05-21 | 2012-09-19 | 焦作聚能能源科技有限公司 | 一种锂离子电池用石墨/LiAlO2/石墨烯复合材料及其制备方法 |
CN103022459A (zh) * | 2012-11-27 | 2013-04-03 | 中国科学院大连化学物理研究所 | 一种石墨烯/钛酸锂复合负极材料的制备方法 |
US20150044556A1 (en) * | 2013-08-08 | 2015-02-12 | Yanbo Wang | Cathode active material-coated discrete graphene sheets for lithium batteries and process for producing same |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NO20190459A1 (en) * | 2019-04-04 | 2020-10-05 | Ipr Holding As | Method for pre-lithiating a lithium-ion capacitor |
NO345255B1 (en) * | 2019-04-04 | 2020-11-23 | Ipr Holding As | Method for pre-lithiating a lithium-ion capacitor |
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