CN105161309A - Lithium ion hybrid capacitor - Google Patents
Lithium ion hybrid capacitor Download PDFInfo
- Publication number
- CN105161309A CN105161309A CN201510589814.8A CN201510589814A CN105161309A CN 105161309 A CN105161309 A CN 105161309A CN 201510589814 A CN201510589814 A CN 201510589814A CN 105161309 A CN105161309 A CN 105161309A
- Authority
- CN
- China
- Prior art keywords
- lithium
- negative electrode
- positive electrode
- active material
- electrode
- 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.)
- Granted
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- 239000003990 capacitor Substances 0.000 title claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 239000007774 positive electrode material Substances 0.000 claims abstract description 25
- 239000007773 negative electrode material Substances 0.000 claims abstract description 21
- 239000011247 coating layer Substances 0.000 claims abstract description 12
- 238000004804 winding Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 20
- 229910021385 hard carbon Inorganic materials 0.000 claims description 12
- 239000004005 microsphere Substances 0.000 claims description 11
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- 229910013716 LiNi Inorganic materials 0.000 claims description 6
- 238000009830 intercalation Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- CJYZTOPVWURGAI-UHFFFAOYSA-N lithium;manganese;manganese(3+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[O-2].[Mn].[Mn+3] CJYZTOPVWURGAI-UHFFFAOYSA-N 0.000 claims description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 2
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 claims 1
- 238000010030 laminating Methods 0.000 claims 1
- 239000006258 conductive agent Substances 0.000 abstract description 8
- 239000011230 binding agent Substances 0.000 abstract description 5
- 210000004027 cell Anatomy 0.000 description 21
- 239000011149 active material Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
一种锂离子混合型电容器，其电芯是由正极电极片、负极电极片和置于正极与负极之间的隔膜通过卷绕或叠片的方式得到的。正极电极片包括正极集流体和涂覆于正极集流体上的正极涂布层，负极电极片包括负极集流体和涂覆于负极集流体上的负极涂布层。正极涂布层包括正极活性物质、导电剂和粘结剂，负极涂布层包括负极活性物质、导电剂和粘结剂。负极的预嵌锂容量为负极在相对于金属锂电极0.01～1.5V电位区间内容量的40～80％，且满足以下关系式：Cn×mn＝n×Cp×mp。
A lithium-ion hybrid capacitor, the cell of which is obtained by winding or stacking a positive electrode sheet, a negative electrode sheet, and a diaphragm placed between the positive electrode and the negative electrode. The positive electrode sheet includes a positive electrode collector and a positive electrode coating layer coated on the positive electrode collector, and the negative electrode sheet includes a negative electrode collector and a negative electrode coating layer coated on the negative electrode collector. The positive electrode coating layer includes a positive electrode active material, a conductive agent and a binder, and the negative electrode coating layer includes a negative electrode active material, a conductive agent and a binder. The pre-intercalated lithium capacity of the negative electrode is 40-80% of the capacity of the negative electrode in the potential range of 0.01-1.5V relative to the metal lithium electrode, and satisfies the following relationship: C n ×m n =n×C p ×m p .
Description
技术领域technical field
本发明涉及一种电化学储能器件，尤其涉及一种锂离子混合型电容器。The invention relates to an electrochemical energy storage device, in particular to a lithium-ion hybrid capacitor.
背景技术Background technique
锂离子电容器是一种新型的功率型储能器件，与锂离子电池相比其高倍率放电和循环寿命更佳，与双电层的超级电容器相比能量密度可以提高3-6倍。但是，锂离子电容器需要在负极预嵌入部分锂，一方面可以补偿负极在化成过程中锂的消耗，另一方面可以调控锂离子电容器在工作中正极和负极的电位，从而使锂离子电容器具有更高的能量密度和更佳的循环寿命。Lithium-ion capacitors are a new type of power-type energy storage device. Compared with lithium-ion batteries, their high-rate discharge and cycle life are better, and their energy density can be increased by 3-6 times compared with electric double-layer supercapacitors. However, lithium-ion capacitors need to pre-embed some lithium in the negative electrode. On the one hand, it can compensate for the lithium consumption of the negative electrode during the formation process, and on the other hand, it can regulate the potential of the positive and negative electrodes of the lithium-ion capacitor during operation, so that the lithium-ion capacitor has more High energy density and better cycle life.
发明内容Contents of the invention
本发明的目的是提供一种锂离子混合型电容器，提高锂离子电容器的能量密度和循环寿命。The object of the present invention is to provide a lithium-ion hybrid capacitor to improve the energy density and cycle life of the lithium-ion capacitor.
为了解决上述技术问题，本发明采用以下技术方案：In order to solve the above technical problems, the present invention adopts the following technical solutions:
锂离子混合型电容器，包括壳体、置于壳体内部的电芯和含浸于电芯内的电解液，所述的电芯是由正极电极片、负极电极片和置于正极电极片与负极电极片之间的隔膜通过卷绕或叠片的方式得到的。所述的正极电极片包括正极集流体和涂覆于正极集流体上的正极涂布层。所述的负极电极片包括负极集流体和涂覆于负极集流体上的负极涂布层。所述的正极涂布层含有正极活性物质，所述的负极涂布层含有负极活性物质。负极电极片的预嵌锂容量为负极活性物质在相对于金属锂电极0.01～1.5V电位区间内容量的40～80％，且满足以下关系式：Lithium-ion hybrid capacitors, including a shell, a cell placed inside the shell, and an electrolyte impregnated in the cell. The cell is composed of a positive electrode sheet, a negative electrode sheet, and a positive electrode sheet and a negative electrode sheet. The separator between the electrode sheets is obtained by winding or lamination. The positive electrode sheet includes a positive current collector and a positive coating layer coated on the positive current collector. The negative electrode sheet includes a negative electrode collector and a negative electrode coating layer coated on the negative electrode collector. The positive electrode coating layer contains positive electrode active materials, and the negative electrode coating layer contains negative electrode active materials. The pre-intercalated lithium capacity of the negative electrode sheet is 40-80% of the capacity of the negative active material in the potential range of 0.01-1.5V relative to the metal lithium electrode, and satisfies the following relationship:
Cn×mn＝n×Cp×mp C n ×m n =n×C p ×m p
其中，Cn为负极活性物质相对于金属锂电极在0.1～0.5V电位区间内的比容量，mn为负极活性物质的质量，Cp为正极活性物质相对于金属锂电极在2.0～4.2V电位区间内的比容量，mp为正极活性物质的质量，n＝1.0～1.2。Among them, C n is the specific capacity of the negative electrode active material relative to the metal lithium electrode in the potential range of 0.1-0.5V, m n is the mass of the negative electrode active material, and C p is the positive electrode active material relative to the metal lithium electrode at 2.0-4.2V. The specific capacity within the potential interval, m p is the mass of the positive electrode active material, n=1.0-1.2.
所述的负极活性物质由硬碳和石墨化中间相碳微球按4:1～9:1的重量比组成。由于硬碳是不规则颗粒形貌，石墨化中间相碳微球是球状，两者按此比例与导电剂混合后堆积最为紧密，并且，具有高比容量的石墨化中间相碳微球被具有高倍率充放电性能的硬碳所包围，可以形成协同效应，既能保证高功率性能、又能有效降低过电位。另外，石墨化中间相碳微球的平台电位相对于金属锂电极在0.2V以下，而硬碳没有明显的充放电平台，采用两者混合制备复合负极，可以在0.2V以下形成锂的类似“蓄水池”效应，一方面可以降低负极电位、提高器件的电压，另一方面防止在低温、大电流嵌锂的情况下在负极表面形成锂的枝状晶。The negative electrode active material is composed of hard carbon and graphitized mesocarbon microspheres in a weight ratio of 4:1˜9:1. Since the hard carbon has an irregular particle shape, the graphitized mesocarbon microspheres are spherical, and the two are mixed with the conductive agent in this proportion to pack the most compactly, and the graphitized mesocarbon microspheres with high specific capacity are Surrounded by hard carbon with high rate charge and discharge performance, it can form a synergistic effect, which can not only ensure high power performance, but also effectively reduce overpotential. In addition, the platform potential of graphitized mesocarbon microspheres is below 0.2V relative to the metal lithium electrode, while hard carbon has no obvious charge-discharge platform. Using the mixture of the two to prepare a composite negative electrode can form a lithium-like electrode below 0.2V. The "reservoir" effect, on the one hand, can reduce the potential of the negative electrode and increase the voltage of the device, and on the other hand, prevent the formation of lithium dendrites on the surface of the negative electrode under the condition of low temperature and high current lithium intercalation.
所述的正极活性材料由可插嵌锂离子的正极材料和电容性碳材料组成，按100质量份计算，可插嵌锂离子的正极材料为0～50质量份，电容性碳材料为50～100质量份，可插嵌锂离子的正极材料为镍钴锰酸锂(LiNixCoyMnzO2)或镍钴铝酸锂(LiNixCoyAlzO2)或钴酸锂(LiCoO2)或锰酸锂(LiMn2O4)，电容性碳材料为活性炭或活性的炭纤维或多孔导电炭黑或石墨烯。The positive electrode active material is composed of a positive electrode material capable of intercalating lithium ions and a capacitive carbon material. Calculated by 100 parts by mass, the positive electrode material capable of intercalating lithium ions is 0 to 50 parts by mass, and the capacitive carbon material is 50 to 50 parts by mass. 100 parts by mass, the positive electrode material that can intercalate lithium ions is lithium nickel cobalt manganese oxide (LiNi x Co y Mn z O 2 ) or lithium nickel cobalt aluminate (LiNi x Co y Al z O 2 ) or lithium cobalt oxide (LiCoO 2 ) or lithium manganate (LiMn 2 O 4 ), the capacitive carbon material is activated carbon or activated carbon fiber or porous conductive carbon black or graphene.
锂离子混合型电容器可按如下步骤制备：将负极电极片、正极电极片和隔膜叠片或卷绕形成电芯，隔膜位于负极电极片与正极电极片之间。将电芯放入壳体中，正极和负极的极耳伸出壳体。金属锂电极放入壳体中，金属锂电极与电芯相对放置并用隔膜隔开。壳体注入过量电解液后，对壳体进行热封口。以金属锂电极作为对电极，对负极预嵌锂，嵌锂容量为负极在相对于金属锂电极0.01～1.5V电位区间内容量的40～80％。最后，取出金属锂电极，倒出多余的电解液，进行真空封口，得到锂离子混合型电容器。The lithium-ion hybrid capacitor can be prepared as follows: a negative electrode sheet, a positive electrode sheet and a separator are laminated or wound to form a battery core, and the separator is located between the negative electrode sheet and the positive electrode sheet. Put the cell into the casing, and the positive and negative tabs protrude out of the casing. The metal lithium electrode is placed in the casing, and the metal lithium electrode is placed opposite to the battery cell and separated by a diaphragm. After the casing is filled with excess electrolyte, the casing is heat-sealed. The metal lithium electrode is used as the counter electrode, and lithium is pre-intercalated to the negative electrode, and the lithium intercalation capacity is 40-80% of the capacity of the negative electrode in the potential range of 0.01-1.5V relative to the metal lithium electrode. Finally, the metal lithium electrode is taken out, the excess electrolyte is poured out, and vacuum sealing is performed to obtain a lithium-ion hybrid capacitor.
附图说明Description of drawings
图1所示为实施例1的负极电极片的扫描电镜照片。FIG. 1 is a scanning electron micrograph of the negative electrode sheet of Example 1.
具体实施方式Detailed ways
本发明将负极电极片、正极电极片和隔在负极电极片与正极电极片之间的隔膜叠片或卷绕形成电芯。电极片的制备采用涂布的方法制成：将包含正极活性物质、导电剂和粘结剂的浆料涂布到含有2％～30％开孔率的贯穿孔的铝箔上，制成正极电极片；将包含负极活性物质、导电剂和粘结剂的浆料涂布到含有2％～30％开孔率的贯穿孔的铜箔或镍箔上，制成负极电极片。In the present invention, the negative electrode sheet, the positive electrode sheet and the separator separated between the negative electrode sheet and the positive electrode sheet are laminated or wound to form a battery core. The preparation of the electrode sheet is made by the method of coating: the slurry containing the positive active material, the conductive agent and the binder is coated on the aluminum foil with a through hole with a porosity of 2% to 30%, and the positive electrode is made sheet; coating the slurry containing the negative electrode active material, the conductive agent and the binder on the copper foil or nickel foil with through holes with an opening ratio of 2% to 30%, to make a negative electrode sheet.
所述的粘结剂选择聚偏氟乙烯(PVDF或聚四氟乙烯(PTFE)或羧甲基纤维素钠(CMC)或丁苯橡胶(SBR)或成都茵地乐产的LA系列水性粘结剂等。所述的导电剂选自导电炭黑或导电石墨或碳纳米管。正极活性材料由锂离子电池正极材料和电容性碳材料组成，按100质量份计算，可插嵌锂离子的正极材料为0～50质量份，电容性材料为50～100质量份，可插嵌锂离子的正极材料为镍钴锰酸锂(LiNixCoyMnzO2)或镍钴铝酸锂(LiNixCoyAlzO2)或钴酸锂(LiCoO2)或锰酸锂(LiMn2O4)。电容性碳材料为活性炭或活性的炭纤维或石墨烯。负极活性材料由硬碳和石墨化中间相碳微球按4:1～9:1的重量比组成。The binder is polyvinylidene fluoride (PVDF or polytetrafluoroethylene (PTFE) or sodium carboxymethyl cellulose (CMC) or styrene-butadiene rubber (SBR) or LA series water-based adhesive produced by Chengdu Yindile. agent, etc. The conductive agent is selected from conductive carbon black or conductive graphite or carbon nanotubes. The positive electrode active material is composed of a lithium ion battery positive electrode material and a capacitive carbon material, calculated by 100 parts by mass, and can insert the positive electrode of lithium ions The material is 0 to 50 parts by mass, the capacitive material is 50 to 100 parts by mass, and the positive electrode material that can intercalate lithium ions is lithium nickel cobalt manganate (LiNi x Co y Mn z O 2 ) or lithium nickel cobalt aluminate (LiNi x Co y Al z O 2 ) or lithium cobaltate (LiCoO 2 ) or lithium manganese oxide (LiMn 2 O 4 ). The capacitive carbon material is activated carbon or activated carbon fiber or graphene. The negative electrode active material is made of hard carbon and graphite The mesophase carbon microspheres are composed at a weight ratio of 4:1 to 9:1.
以下结合实施例对本发明作进一步说明。The present invention will be further described below in conjunction with embodiment.
实施例1Example 1
正极电极片的活性材料为活性炭，正极集流体为开孔率为20％的贯穿孔的铝箔。负极电极片的活性材料为硬碳和石墨化中间相碳微球按4：1组成，负极集流体为开孔率为20％的贯穿孔的铜箔。隔膜为celgard2400。10片正极电极片和10片负极电极片叠片制成电芯。其中，负极活性材料在0.1～0.5V电位区间内的比容量为80mAh/g，正极活性炭在2.0～4.2V电位区间内的比容量为50mAh/g，取n＝1.2，正、负极活性物质的质量之比为1.33：1。将电芯和金属锂电极放入盛有电解液的密闭容器中浸渍，电解液为1mol/LLiPF6的溶液，溶剂为体积比为1:1:1的碳酸乙烯酯、碳酸二甲酯和碳酸二乙酯的混合溶剂。将电芯放入壳体中，正极和负极的极耳伸出壳体。金属锂电极放入壳体中，金属锂电极与电芯相对放置并用隔膜隔开。壳体注入过量电解液后，对壳体进行热封口。以金属锂电极作为对电极，对负极预嵌锂。由于负极在相对于金属锂电极0.01～1.5V电位区间内容量为240mAh/g，因此预嵌锂容量为240mAh/g×80％＝192mAh/g。最后，取出金属锂电极，倒出多余的电解液，进行真空封口，得到锂离子混合型电容器。采用武汉兰电公司CT2001A的电池测试仪测试，该锂离子混合型电容器的能量密度为18Wh/g基于整个器件的质量，20CA倍率下充放电循环10000周容量保持率为93％。其中CA的意义，根据《QB/T2502-2000锂离子蓄电池总规范》，C表示电池以5h率放电至终止电压时的容量，20CA则表示20倍容量的电流。以下实施例也采用了同一测试设备测试。图1所示为负极电极片的扫描电镜照片，球形颗粒为石墨化中间相碳微球，不规则颗粒为硬碳，链状纳米颗粒为导电剂，可以看到，石墨化中间相碳微球被硬碳和导电剂包围，堆积紧密。The active material of the positive electrode sheet is activated carbon, and the positive current collector is aluminum foil with through holes with an opening ratio of 20%. The active material of the negative electrode sheet is composed of hard carbon and graphitized mesocarbon microspheres in a ratio of 4:1, and the negative current collector is a through-hole copper foil with a porosity of 20%. The separator is celgard2400. 10 positive electrode sheets and 10 negative electrode sheets are laminated to make a cell. Among them, the specific capacity of the negative active material is 80mAh/g in the potential range of 0.1-0.5V, and the specific capacity of the positive activated carbon in the potential range of 2.0-4.2V is 50mAh/g, taking n=1.2, the positive and negative active materials The mass ratio is 1.33:1. Put the battery cell and metal lithium electrode into a closed container filled with electrolyte for immersion. The electrolyte is a solution of 1mol/LLiPF 6 , and the solvent is ethylene carbonate, dimethyl carbonate and carbonic acid with a volume ratio of 1:1:1. A mixed solvent of diethyl ester. Put the cell into the casing, and the positive and negative tabs protrude out of the casing. The metal lithium electrode is placed in the casing, and the metal lithium electrode is placed opposite to the battery cell and separated by a diaphragm. After the casing is filled with excess electrolyte, the casing is heat-sealed. A metal lithium electrode is used as a counter electrode, and lithium is pre-intercalated to the negative electrode. Since the negative electrode has a capacity of 240mAh/g in the potential range of 0.01-1.5V relative to the metal lithium electrode, the pre-intercalated lithium capacity is 240mAh/g×80%=192mAh/g. Finally, the metal lithium electrode is taken out, the excess electrolyte is poured out, and vacuum sealing is performed to obtain a lithium-ion hybrid capacitor. Tested with the CT2001A battery tester of Wuhan Landian Company, the energy density of the lithium-ion hybrid capacitor is 18Wh/g based on the mass of the entire device, and the capacity retention rate of 10,000 cycles of charging and discharging at a rate of 20CA is 93%. The meaning of CA, according to "QB/T2502-2000 General Specifications for Lithium-ion Batteries", C indicates the capacity of the battery when it is discharged to the termination voltage at a rate of 5h, and 20CA indicates the current of 20 times the capacity. The following examples are also tested with the same test equipment. Figure 1 shows the scanning electron microscope photo of the negative electrode sheet. The spherical particles are graphitized mesocarbon microspheres, the irregular particles are hard carbon, and the chain nanoparticles are conductive agents. It can be seen that the graphitized mesocarbon microspheres Surrounded by hard carbon and conductive agent, packed tightly.
对比例comparative example
正极电极片的活性材料活性炭，正极集流体为开孔率为20％的贯穿孔的铝箔。负极电极片的活性材料为硬碳，负极集流体为开孔率为20％的贯穿孔的铜箔。隔膜为celgard2400，10片正极电极片和10片负极电极片叠片制成电芯。其中，负极活性材料在0.1～0.5V电位区间内的比容量为60mAh/g，正极活性炭在2.0～4.2V电位区间内的比容量为50mAh/g，取n＝1.2，正、负极活性物质的质量之比为1：1。将电芯和金属锂电极放入盛有电解液的密闭容器中浸渍，电解液为1mol/LLiPF6的溶液，溶剂为体积比为1:1:1的碳酸乙烯酯、碳酸二甲酯和碳酸二乙酯的混合溶剂。将电芯放入壳体中，正极和负极的极耳伸出壳体；金属锂电极放入壳体中，金属锂电极与电芯相对放置并用隔膜隔开。壳体注入过量电解液后，对壳体进行热封口。以金属锂电极作为对电极，对负极预嵌锂。由于负极在相对于金属锂电极0.01～1.5V电位区间内容量为200mAh/g，因此预嵌锂容量为200mAh/g×80％＝160mAh/g。最后，取出金属锂电极，倒出多余的电解液，进行真空封口，得到锂离子混合型电容器。该锂离子混合型电容器能量密度为12Wh/g基于整个器件的质量，20CA倍率下充放电循环10000周容量保持率为80％。The active material of the positive electrode sheet is activated carbon, and the positive current collector is an aluminum foil with through holes with a porosity of 20%. The active material of the negative electrode sheet is hard carbon, and the negative current collector is a through-hole copper foil with a porosity of 20%. The diaphragm is celgard2400, and 10 positive electrode sheets and 10 negative electrode sheets are stacked to make the cell. Among them, the specific capacity of the negative electrode active material is 60mAh/g in the potential range of 0.1-0.5V, and the specific capacity of the positive activated carbon in the potential range of 2.0-4.2V is 50mAh/g, taking n=1.2, the positive and negative active materials The mass ratio is 1:1. Put the battery cell and metal lithium electrode into a closed container filled with electrolyte for immersion. The electrolyte is a solution of 1mol/LLiPF 6 , and the solvent is ethylene carbonate, dimethyl carbonate and carbonic acid with a volume ratio of 1:1:1. A mixed solvent of diethyl ester. Put the cell into the casing, and the tabs of the positive and negative electrodes protrude from the casing; the metal lithium electrode is put into the casing, and the metal lithium electrode is placed opposite to the cell and separated by a diaphragm. After the casing is filled with excess electrolyte, the casing is heat-sealed. A metal lithium electrode is used as a counter electrode, and lithium is pre-intercalated to the negative electrode. Since the negative electrode has a capacity of 200mAh/g in the potential range of 0.01-1.5V relative to the metal lithium electrode, the pre-intercalated lithium capacity is 200mAh/g×80%=160mAh/g. Finally, the metal lithium electrode is taken out, the excess electrolyte is poured out, and vacuum sealing is performed to obtain a lithium-ion hybrid capacitor. The lithium-ion hybrid capacitor has an energy density of 12Wh/g based on the mass of the entire device, and a capacity retention rate of 80% for 10,000 cycles of charging and discharging at a rate of 20CA.
实施例2Example 2
正极电极片的活性材料为质量比为3:1的活性炭和镍钴锰酸锂，正极集流体为开孔率为30％的贯穿孔的铝箔。负极电极片的活性材料为硬碳和石墨化中间相碳微球按9：1组成，负极集流体为开孔率为30％的贯穿孔的镍箔。隔膜为celgard2400。正极电极片和负极电极片卷绕后热压制成方形电芯。其中，负极活性材料在0.1～0.5V电位区间内的比容量为60mAh/g，正极活性材料在2.0～4.2V电位区间内的比容量为70mAh/g，取n＝1.0，正、负极活性物质的质量之比为0.86：1。将电芯和金属锂电极放入盛有电解液的密闭容器中浸渍，电解液为1mol/LLiPF6的溶液，溶剂为体积比为1:1:1的碳酸乙烯酯、碳酸二甲酯和碳酸二乙酯的混合溶剂。将电芯放入壳体中，正极和负极的极耳伸出壳体；金属锂电极放入壳体中，金属锂电极与电芯相对放置并用隔膜隔开。壳体注入过量电解液后，对壳体进行热封口。以金属锂电极作为对电极，对负极预嵌锂。由于负极在相对于金属锂电极0.01～1.5V电位区间内容量为210mAh/g，因此预嵌锂容量为210mAh/g×60％＝126mAh/g。最后，取出金属锂电极，倒出多余的电解液，进行真空封口，得到锂离子混合型电容器。测试得到该锂离子混合型电容器的能量密度为30Wh/g基于整个器件的质量，20A倍率下充放电循环10000周容量保持率为87％。The active material of the positive electrode sheet is activated carbon and nickel-cobalt lithium manganese oxide with a mass ratio of 3:1, and the positive current collector is aluminum foil with through-holes with a porosity of 30%. The active material of the negative electrode sheet is composed of hard carbon and graphitized mesocarbon microspheres at a ratio of 9:1, and the negative current collector is a through-hole nickel foil with a porosity of 30%. The diaphragm is celgard2400. The positive electrode sheet and the negative electrode sheet are wound and hot-pressed to form a square cell. Among them, the specific capacity of the negative active material is 60mAh/g in the potential range of 0.1-0.5V, and the specific capacity of the positive active material in the potential range of 2.0-4.2V is 70mAh/g, taking n=1.0, the positive and negative active materials The mass ratio is 0.86:1. Put the battery cell and metal lithium electrode into a closed container filled with electrolyte for immersion. The electrolyte is a solution of 1mol/LLiPF 6 , and the solvent is ethylene carbonate, dimethyl carbonate and carbonic acid with a volume ratio of 1:1:1. A mixed solvent of diethyl ester. Put the cell into the case, and the tabs of the positive and negative electrodes protrude out of the case; the metal lithium electrode is placed in the case, and the metal lithium electrode is placed opposite to the cell and separated by a diaphragm. After the casing is filled with excess electrolyte, the casing is heat-sealed. A metal lithium electrode is used as a counter electrode, and lithium is pre-intercalated to the negative electrode. Since the negative electrode has a capacity of 210mAh/g in the potential range of 0.01-1.5V relative to the metal lithium electrode, the pre-intercalated lithium capacity is 210mAh/g×60%=126mAh/g. Finally, the metal lithium electrode is taken out, the excess electrolyte is poured out, and vacuum sealing is performed to obtain a lithium-ion hybrid capacitor. The test shows that the energy density of the lithium-ion hybrid capacitor is 30Wh/g based on the mass of the entire device, and the capacity retention rate of 10,000 cycles of charging and discharging at a rate of 20A is 87%.
实施例3Example 3
正极电极片的活性材料按100质量份计，为镍钴铝酸锂20质量份、钴酸锂20质量份、锰酸锂10质量份、活性炭40质量份、活性的炭纤维5质量份、石墨烯5质量份；正极集流体为开孔率为30％的贯穿孔的铝箔。负极电极片的活性材料为硬碳和石墨化中间相碳微球按6：1组成，负极集流体为开孔率为30％的贯穿孔的镍箔。隔膜为celgard2400。正极电极片和负极电极片卷绕后热压制成方形电芯。其中，负极活性材料在0.1～0.5V电位区间内的比容量为60mAh/g，正极活性材料在2.0～4.2V电位区间内的比容量为100mAh/g，取n＝1.0，正、负极活性物质的质量之比为0.6：1。将电芯和金属锂电极放入盛有电解液的密闭容器中浸渍，电解液为1mol/LLiPF6的溶液，溶剂为体积比为1:1:1的碳酸乙烯酯、碳酸二甲酯和碳酸二乙酯的混合溶剂。将电芯放入壳体中，正极和负极的极耳伸出壳体；金属锂电极放入壳体中，金属锂电极与电芯相对放置并用隔膜隔开。壳体注入过量电解液后，对壳体进行热封口；以金属锂电极作为对电极，对负极预嵌锂。由于负极在相对于金属锂电极0.01～1.5V电位区间内容量为210mAh/g，因此预嵌锂容量为240mAh/g×40％＝96mAh/g。最后，取出金属锂电极，倒出多余的电解液，进行真空封口，得到锂离子混合型电容器，测试得到该锂离子混合型电容器的能量密度为50Wh/g基于整个器件的质量，20A倍率下充放电循环10000周容量保持率为82％。The active material of the positive electrode sheet is based on 100 parts by mass, which is 20 parts by mass of lithium nickel cobalt aluminate, 20 parts by mass of lithium cobaltate, 10 parts by mass of lithium manganate, 40 parts by mass of activated carbon, 5 parts by mass of activated carbon fiber, graphite 5 parts by mass of alkene; the positive electrode current collector is a through-hole aluminum foil with a porosity of 30%. The active material of the negative electrode sheet is composed of hard carbon and graphitized mesocarbon microspheres at a ratio of 6:1, and the negative current collector is a through-hole nickel foil with a porosity of 30%. The diaphragm is celgard2400. The positive electrode sheet and the negative electrode sheet are wound and hot-pressed to form a square cell. Among them, the specific capacity of the negative electrode active material is 60mAh/g in the potential range of 0.1-0.5V, and the specific capacity of the positive electrode active material in the potential range of 2.0-4.2V is 100mAh/g, taking n=1.0, the positive and negative active materials The mass ratio is 0.6:1. Put the battery cell and metal lithium electrode into a closed container filled with electrolyte for immersion. The electrolyte is a solution of 1mol/LLiPF 6 , and the solvent is ethylene carbonate, dimethyl carbonate and carbonic acid with a volume ratio of 1:1:1. A mixed solvent of diethyl ester. Put the cell into the casing, and the tabs of the positive and negative electrodes protrude from the casing; the metal lithium electrode is put into the casing, and the metal lithium electrode is placed opposite to the cell and separated by a diaphragm. After the casing is injected with excess electrolyte, the casing is heat-sealed; the metal lithium electrode is used as the counter electrode, and lithium is pre-intercalated to the negative electrode. Since the negative electrode has a capacity of 210mAh/g in the potential range of 0.01-1.5V relative to the metal lithium electrode, the pre-intercalated lithium capacity is 240mAh/g×40%=96mAh/g. Finally, take out the metal lithium electrode, pour out the excess electrolyte, and vacuum seal to obtain a lithium-ion hybrid capacitor. The energy density of the lithium-ion hybrid capacitor is tested to be 50Wh/g based on the mass of the entire device. Charged at a rate of 20A The capacity retention rate of 10000 cycles of discharge is 82%.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510589814.8A CN105161309B (en) | 2015-09-16 | 2015-09-16 | Lithium ion hybrid capacitors |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510589814.8A CN105161309B (en) | 2015-09-16 | 2015-09-16 | Lithium ion hybrid capacitors |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105161309A true CN105161309A (en) | 2015-12-16 |
| CN105161309B CN105161309B (en) | 2017-11-14 |
Family
ID=54802132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510589814.8A Active CN105161309B (en) | 2015-09-16 | 2015-09-16 | Lithium ion hybrid capacitors |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105161309B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106206075A (en) * | 2016-06-22 | 2016-12-07 | 凌容新能源科技（上海）有限公司 | Electrode preparation method and super lithium capacitor fabrication method |
| CN106356199A (en) * | 2016-11-10 | 2017-01-25 | 上海奥威科技开发有限公司 | Lithium titanate supercapacitor with good linear charging and discharging behaviors |
| CN107633957A (en) * | 2017-08-03 | 2018-01-26 | 凌容新能源科技（上海）股份有限公司 | Lithium-ion capacitor preparation method and lithium-ion capacitor |
| CN108428563A (en) * | 2018-03-19 | 2018-08-21 | 中国科学院电工研究所 | A kind of lithium ion battery capacitance |
| CN112289592A (en) * | 2020-09-17 | 2021-01-29 | 中国科学院山西煤炭化学研究所 | Lithium ion capacitor and preparation method thereof |
| CN112435861A (en) * | 2020-10-16 | 2021-03-02 | 惠州亿纬锂能股份有限公司 | Positive electrode of hybrid capacitor and preparation method and application thereof |
| CN115148508A (en) * | 2022-08-08 | 2022-10-04 | 凌容新能源科技（上海）股份有限公司 | Energy storage capacitor and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090161296A1 (en) * | 2005-12-08 | 2009-06-25 | Fuji Jukogyo Kabushiki Kaisha | Lithium ion capacitor |
| CN104008893A (en) * | 2014-04-11 | 2014-08-27 | 中国科学院电工研究所 | Manufacturing method of lithium ion mixed type capacitor and lithium ion mixed type capacitor |
| CN104037458A (en) * | 2014-05-16 | 2014-09-10 | 中国科学院电工研究所 | Manufacturing method of lithium ion energy storage device |
| CN104835652A (en) * | 2015-03-24 | 2015-08-12 | 中航锂电（洛阳）有限公司 | Lithium-intercalation negative pole piece used for lithium super-capacitor battery, method for preparing same, and lithium super-capacitor battery |
-
2015
- 2015-09-16 CN CN201510589814.8A patent/CN105161309B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090161296A1 (en) * | 2005-12-08 | 2009-06-25 | Fuji Jukogyo Kabushiki Kaisha | Lithium ion capacitor |
| CN104008893A (en) * | 2014-04-11 | 2014-08-27 | 中国科学院电工研究所 | Manufacturing method of lithium ion mixed type capacitor and lithium ion mixed type capacitor |
| CN104037458A (en) * | 2014-05-16 | 2014-09-10 | 中国科学院电工研究所 | Manufacturing method of lithium ion energy storage device |
| CN104835652A (en) * | 2015-03-24 | 2015-08-12 | 中航锂电（洛阳）有限公司 | Lithium-intercalation negative pole piece used for lithium super-capacitor battery, method for preparing same, and lithium super-capacitor battery |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106206075A (en) * | 2016-06-22 | 2016-12-07 | 凌容新能源科技（上海）有限公司 | Electrode preparation method and super lithium capacitor fabrication method |
| CN106356199A (en) * | 2016-11-10 | 2017-01-25 | 上海奥威科技开发有限公司 | Lithium titanate supercapacitor with good linear charging and discharging behaviors |
| CN107633957A (en) * | 2017-08-03 | 2018-01-26 | 凌容新能源科技（上海）股份有限公司 | Lithium-ion capacitor preparation method and lithium-ion capacitor |
| CN108428563A (en) * | 2018-03-19 | 2018-08-21 | 中国科学院电工研究所 | A kind of lithium ion battery capacitance |
| CN112289592A (en) * | 2020-09-17 | 2021-01-29 | 中国科学院山西煤炭化学研究所 | Lithium ion capacitor and preparation method thereof |
| CN112435861A (en) * | 2020-10-16 | 2021-03-02 | 惠州亿纬锂能股份有限公司 | Positive electrode of hybrid capacitor and preparation method and application thereof |
| CN115148508A (en) * | 2022-08-08 | 2022-10-04 | 凌容新能源科技（上海）股份有限公司 | Energy storage capacitor and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105161309B (en) | 2017-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110660965B (en) | Negative plate and preparation method thereof, lithium ion battery and preparation method and application thereof | |
| CN104008893B (en) | Preparation method of lithium-ion hybrid capacitor and lithium-ion hybrid capacitor | |
| WO2021057428A1 (en) | Secondary battery and battery module, battery pack and device containing same | |
| CN105161309B (en) | Lithium ion hybrid capacitors | |
| WO2020177623A1 (en) | Negative pole piece, secondary battery and apparatus thereof | |
| CN104347880A (en) | Fast-charge Li-ion battery | |
| WO2021008429A1 (en) | Secondary battery, and battery module, battery pack and device related thereto | |
| WO2014134967A1 (en) | Positive electrode film of lithium ion battery and preparation and application therefor | |
| CN104953186B (en) | The preparation technology and negative pole of a kind of lithium ion battery mend lithium device | |
| CN102694200A (en) | Silicon-based negative lithium-ion battery and manufacturing method thereof | |
| CN115842096B (en) | Pre-lithiation pole piece and preparation method thereof, secondary battery and electric device | |
| CN102800841A (en) | Negative plate, lithium ion battery and preparation method thereof | |
| WO2020118880A1 (en) | Graphite positive electrode and zinc negative electrode-based hybrid super capacitor | |
| CN106169617A (en) | A kind of space safety high power lithium ion accumulator | |
| CN102013469A (en) | Lithium-ion secondary battery and its positive pole piece | |
| CN103762335B (en) | Lithium titanate electrode plate and lithium ion battery | |
| CN115810718A (en) | Negative electrode sheet and secondary battery including same | |
| CN107248451A (en) | A kind of lithium-ion capacitor of high-energy-density | |
| CN101262056A (en) | An aqueous solution rechargeable lithium-ion battery | |
| CN115312692A (en) | Lithium-rich composite pole piece for positive electrode and preparation method and application thereof | |
| CN109786841B (en) | A kind of preparation method of lithium ion electrochemical energy storage device | |
| CN105761944B (en) | A kind of hybrid super capacitor anode composite piece and preparation method thereof, hybrid super capacitor | |
| CN105047418B (en) | A kind of lithium titanate base lithium ion capacitor | |
| CN115036444A (en) | A kind of pre-lithiated, pre-sodiumized composite negative electrode material and its preparation method and application | |
| CN108428563B (en) | A lithium ion battery capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |