CN106848397A - A kind of lithium-ion capacitor electrolyte - Google Patents
A kind of lithium-ion capacitor electrolyte Download PDFInfo
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- CN106848397A CN106848397A CN201611199546.XA CN201611199546A CN106848397A CN 106848397 A CN106848397 A CN 106848397A CN 201611199546 A CN201611199546 A CN 201611199546A CN 106848397 A CN106848397 A CN 106848397A
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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Abstract
The present invention relates to a kind of lithium-ion capacitor electrolyte, belong to energy storage device technical field.With carbonic ester as solvent, with lithium salts and organic salt as solute, lithium salts and organic salt molar concentration in the electrolytic solution are 1.6 2.0M to the lithium-ion capacitor electrolyte.Lithium-ion capacitor electrolyte middle and high concentration lithium salts of the present invention is mainly used in shortening the diffusion length of lithium ion, alleviates the loss of cyclic process lithium salts；And high concentration organic salt is then mainly used in the energy stores of anode electrode, ultimately facilitates and realize lithium-ion capacitor high power capacity, low internal resistance, long-life use characteristic.
Description
Technical field
The present invention relates to a kind of electrolyte, more particularly to a kind of lithium-ion capacitor electrolyte, belong to energy storage device skill
Art field.
Background technology
Lithium-ion capacitor has the new of double layer capacitor power characteristic and lithium ion battery energy advantage concurrently as a kind of
Type energy storage device, receives the extensive concern of academia and industrial quarters, it is considered to be ultracapacitor of new generation and lithium-ion electric
The prior development direction (energy density reaches 10-20Wh/kg, and power density reaches 1-5kW/kg) in pond.
Under normal circumstances, lithium-ion capacitor refers to that positive electrode active material is high specific energy activated carbon, and negative electrode active material is Gao Rong
Carbon Materials composition (such as Delanium, soft charcoal, hard charcoal) of amount.However, the research for the device is concentrated mainly at this stage
Electrode material and the aspect of technology for preparing electrode mode two, then study relatively in terms of the electrolyte of capacitor important component
It is few.
Additionally, the research for electrolyte is concentrated mainly on the aspects such as high pressure resistant, gassing inhibitors, film forming agent at this stage
Research, lithium-ion capacitor energy storage characteristic is combined, (positive pole is that, based on electric double layer absorption principle energy storage, negative pole is to be based on oxidation also
Original reaction energy storage) novel electrolyte research it is then relatively fewer.Therefore, electrolyte at this stage be difficult to meet high power capacity, it is low in
Resistance, the preparation and production requirement of long-life lithium-ion capacitor.
The content of the invention
The purpose of the present invention is directed to the above-mentioned problems in the prior art, it is proposed that one kind can meet high power capacity, low
Internal resistance, the electrolyte of long-life lithium-ion capacitor.
The purpose of the present invention can be realized by following technical proposal：A kind of lithium-ion capacitor electrolyte, the electricity
With carbonic ester as solvent, with lithium salts and organic salt as solute, lithium salts and organic salt molar concentration in the electrolytic solution are solution liquid
1.6-2.0M。
Lithium salts and organic salt comprising high concentration in electrolyte of the present invention, wherein, high concentration lithium salts is mainly used in shortening lithium
The diffusion length of ion, alleviates the loss of cyclic process lithium salts；And high concentration organic salt is then mainly used in the energy of anode electrode
Storage, ultimately facilitates and realizes lithium-ion capacitor high power capacity, low internal resistance, long-life use characteristic.
In a kind of above-mentioned lithium-ion capacitor electrolyte, the carbonic ester is makrolon, diethyl carbonate, carbon
At least one in vinyl acetate, methyl ethyl carbonate, dimethyl carbonate, vinylene carbonate.
In a kind of above-mentioned lithium-ion capacitor electrolyte, the carbonic ester is 35-44wt% by mass percent
Ethylene carbonate, the methyl ethyl carbonate of 35-44wt%, the dimethyl carbonate of 10-25wt%, the vinylene carbonate of 1-2wt%
Ester is constituted.This fit system is based on the electrical conductivity of electrolyte, proof voltage and compatible and real with positive and negative electrode material
What checking was obtained.
In a kind of above-mentioned lithium-ion capacitor electrolyte, the lithium salts is LiPF6、LiBF4、LiClO4In extremely
Few one kind.
In a kind of above-mentioned lithium-ion capacitor electrolyte, the organic salt is SBP-BF4、TEA-BF4、TEMA-
BF4In at least one.
In a kind of above-mentioned lithium-ion capacitor electrolyte, the preparation method of the electrolyte is：Lithium salts is added
Add organic salt to be well mixed after being well mixed in carbonate solvent, be configured to electrolyte.
In a kind of above-mentioned lithium-ion capacitor electrolyte, the preparation process of the electrolyte is less than in moisture
1ppm, oxygen content are carried out in the environment of being less than 0.1ppm.
In a kind of above-mentioned lithium-ion capacitor electrolyte, the temperature of the electrolyte in the preparation process is 40-
60℃。
Selected raw material are industrial scale product in electrolyte of the present invention, and preparation process only needs control operation ring
The moisture in border, oxygen content, mixing temperature, incorporation time and mixing rotating speed etc., operating process is simple, low production cost,
It is easily achieved production in enormous quantities.
Preferably, the lithium-ion capacitor electrolyte is applied in lithium-ion capacitor.
Preferably, the cathode size of the lithium-ion capacitor by following mass percent into being grouped into：Conductive agent：2-
10%, binding agent：3-5%, dispersant：3-5%, carbon cathode material：Surplus；Wherein, the solid content of cathode size is 20-
30wt%.
Preferably, the carbon cathode material is one or more in Delanium, native graphite, soft charcoal, hard charcoal.
Preferably, the anode sizing agent of the lithium-ion capacitor by following mass percent into being grouped into：Conductive agent：4-
10%, binding agent：3-5%, dispersant：2-5%, absorbent charcoal material：Surplus；Wherein, the viscosity of anode sizing agent is 900-
1500cps。
By above-mentioned positive and negative electrode slurry be coated on corrosive aluminum foil formed electrode after through drying, roll, be punched after acquisition (50-
60) the positive and negative electrode pole piece of mm* (70-80) mm.
Cathode pole piece, cellulosic separator, anode pole piece, cellulosic separator are assembled into lithium according to " Z-type " lamination process again
The battery core of ionistor.Meanwhile, the metal lithium sheet into certain size is folded in the barrier film exterior measuring for closing on outermost layer cathode pole piece, with
Above-mentioned battery core is assembled into the final battery core of lithium-ion capacitor.After the final battery core is put into the aluminum plastic membrane shell of certain size
Above-mentioned electrolyte is injected, vacuum-pumping density is honored as a queen and can obtain lithium-ion capacitor.
Compared with prior art, the present invention has following advantage：
1. lithium salts and organic salt comprising high concentration in electrolyte of the present invention, are advantageously implemented lithium-ion capacitor Gao Rong
Amount, low internal resistance, long-life use characteristic.
2. electrolyte preparation process of the present invention is simple, low production cost, it is easy to accomplish produce in enormous quantities.
Specific embodiment
The following is specific embodiment of the invention, technical scheme is further described, but the present invention is simultaneously
It is not limited to these embodiments.
Embodiment 1：
Under glove box environment in moisture less than 1ppm, oxygen content less than 0.1ppm, by solute LiPF6Be added to by
Ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, vinylene carbonate according to mass percent be respectively 35wt%,
In the double solvents of 44wt%, 20wt%, 1wt% composition, stirred under the conditions of 100rmp stir speed (S.S.)s and 60 DEG C of mixing temperatures
6h.After the mixing of above-mentioned mixed liquor is homogeneous, SBP-BF is added thereto to4Salt, and it is uniform under conditions of 60 DEG C, 100rmp
Mixing 2h, you can obtain lithium-ion capacitance electrolyte, LiPF in electrolyte6And SBP-BF4The molar concentration of salt is 2.0M.
Embodiment 2：
Under glove box environment in moisture less than 1ppm, oxygen content less than 0.1ppm, by solute LiBF4Be added to by
Ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, vinylene carbonate by mass percentage be respectively 40wt%,
In the double solvents of 44wt%, 14wt%, 2wt% composition, stirred under the conditions of 80rmp stir speed (S.S.)s and 50 DEG C of mixing temperatures
5h.After the mixing of above-mentioned mixed liquor is homogeneous, SBP-BF is added thereto to4Salt, and it is uniform under conditions of 60 DEG C, 80rmp
Mixing 3h, you can obtain lithium-ion capacitance electrolyte, LiPF in electrolyte4Molar concentration be 1.8M, SBP-BF4Salt rubs
Your concentration is 2.0M.
Embodiment 3：
Under glove box environment in moisture less than 1ppm, oxygen content less than 0.1ppm, by solute LiPF6Be added to by
Ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, vinylene carbonate by mass percentage be respectively 44wt%,
In the double solvents of 40wt%, 15wt%, 1wt% composition, stirred under the conditions of 200rmp stir speed (S.S.)s and 40 DEG C of mixing temperatures
8h.After the mixing of above-mentioned mixed liquor is homogeneous, TEMA-BF is added thereto to4Salt, and it is uniform under conditions of 50 DEG C, 50rmp
Mixing 2h, you can obtain lithium-ion capacitance electrolyte, LiPF in electrolyte6Molar concentration be 1.6M, TEMA-BF4Salt rubs
Your concentration is 2.0M.
Application Example 1-3：
Electrolyte obtained in above-described embodiment 1-3 is applied in lithium-ion capacitor, the assembling of lithium-ion capacitor
Cheng Wei：
It is 90 according to mass ratio by soft charcoal, butadiene-styrene rubber, sodium cellulose glycolate, conductive black:3:3:4 carry out vacuum stirs
Mix the cathode size for being mixed to get that solid content is 25wt%.Gained cathode size is coated uniformly on corrosive aluminum foil, through drying,
Roll, cut, be punched after can obtain the cathode pole piece of 55mm*75mm.
It is 85 according to mass fraction ratio by activated carbon, conductive black, butadiene-styrene rubber, sodium cellulose glycolate:10:3:2 enter
Row is stirred under vacuum the anode sizing agent for being mixed to get that viscosity is 1200cps.Gained anode sizing agent is coated in corrosive aluminum foil, through dry
It is dry, roll, be punched after obtain 55mm*75mm anode pole piece.
By cathode pole piece, cellulosic separator, anode pole piece, cellulosic separator according to " Z-type " lamination process be assembled into lithium from
The battery core of sub-capacitor.Meanwhile, the metal lithium sheet into certain size is folded in the barrier film exterior measuring for closing on outermost layer cathode pole piece, it is and upper
State the final battery core that battery core is assembled into lithium-ion capacitor.The final battery core is put into the aluminum plastic membrane shell of certain size and is divided afterwards
Not Zhu Ru gained electrolyte in embodiment 1-3, vacuum-pumping density is honored as a queen and can obtain lithium-ion capacitor.
Negative pole and metal lithium electrode in above-mentioned lithium-ion capacitor are carried out into 3 constant current charge and discharges between 0.01C, 0-2.2V
The pre-embedding lithium processes of electricity.Then the test of capacity, internal resistance and cycle life is carried out to it, test result is as shown in table 1.
Table 1
As known from Table 1：Electrolyte of the present invention can realize lithium-ion capacitor high power capacity, low internal resistance, long-life use
Characteristic.
In above-described embodiment and its alternative, solvent can also be makrolon, diethyl carbonate, ethylene carbonate
Ester, methyl ethyl carbonate, dimethyl carbonate, vinylene carbonate, or be makrolon, diethyl carbonate, ethylene carbonate, carbon
Any two kinds, three kinds, four kinds, five kinds and six kinds of mixing in sour methyl ethyl ester, dimethyl carbonate, vinylene carbonate.
In above-described embodiment and its alternative, solvent is ethylene carbonate, methyl ethyl carbonate, dimethyl carbonate, carbon
During the mixing that four kinds of sour vinylene, four mass percent can also be 44wt%, 35wt%, 20wt%, 1wt%,
44wt%, 44wt%, 10wt%, 2wt%, 37wt%, 37wt%, 25wt%, 1wt%, 38wt%, 42wt%, 18wt%,
2wt%, 44wt%, 36wt%, 18wt%, 2wt%, 42wt%, 35wt%, 22wt%, 1wt%, 38wt%, 40wt%,
20wt%, 2wt%.
In above-described embodiment and its alternative, lithium salts can also be LiClO4, or LiPF6、LiBF4、LiClO4In
Any two kinds and three kinds of mixing.
In above-described embodiment and its alternative, organic salt can also be TEA-BF4, or SBP-BF4、TEA-BF4、
TEMA-BF4In any two kinds and three kinds of mixing.
In above-described embodiment and its alternative, the temperature of the electrolyte in preparation process can also for 41 DEG C, 42 DEG C,
43℃、44℃、45℃、46℃、47℃、48℃、49℃、51℃、52℃、53℃、54℃、55℃、56℃、57℃、58℃、59
℃。
In above-described embodiment and its alternative, mixing speed in the mixed process of lithium salts can also for 50rmp,
55rmp、60rmp、65rmp、70rmp、75rmp、85rmp、90rmp、95rmp、105rmp、110rmp、115rmp、120rmp、
125rmp、130rmp、135rmp、140rmp、145rmp、150rmp、155rmp、160rmp、165rmp、170rmp、175rmp、
180rmp, 185rmp, 190rmp, 195rmp, mixing time can also be 4h, 4.5h, 5.5h, 6.5h, 7h, 7.5h.
In above-described embodiment and its alternative, mixing speed in the mixed process of organic salt can also for 55rmp,
60rmp、65rmp、70rmp、75rmp、85rmp、90rmp、95rmp、105rmp、110rmp、115rmp、120rmp、125rmp、
130rmp、135rmp、140rmp、145rmp、150rmp、155rmp、160rmp、165rmp、170rmp、175rmp、180rmp、
185rmp, 190rmp, 195rmp, 200rmp, mixing time can also be 2.5h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h.
In above-described embodiment and its alternative, in electrolyte the molar concentration of lithium salts can also for 1.65M, 1.7M,
1.75M、1.85M、1.9M、1.95M。
In above-described embodiment and its alternative, in electrolyte the molar concentration of organic salt can also for 1.6M,
1.65M、1.7M、1.75M、1.8M、1.85M、1.9M、1.95M。
In above-mentioned Application Example and its alternative, carbon cathode material, binding agent, dispersant, the quality of conductive agent
Percentage can also be 92:3:3:2、91:3:3:3、90:4:4:2、90:5:3:2、90:3:5:2、90:3:3:4、90:4:3:3、
89:5:3:3、85:5:5:5、84:3:3:10。
In above-mentioned Application Example and its alternative, the solid content of cathode size can also for 20wt%, 21wt%,
22wt%, 23wt%, 24wt%, 26wt%, 27wt%, 28wt%, 29wt%, 30wt%.
In above-mentioned Application Example and its alternative, carbon cathode material can also be Delanium, native graphite, hard
Any several mixing in charcoal, or Delanium, native graphite, soft charcoal, hard charcoal.
In above-mentioned Application Example and its alternative, absorbent charcoal material, conductive agent, binding agent, the quality of dispersant
Percentage can also be 91:4:3:2、90:4:3:3、90:5:3:2、90:4:4:2、87:6:4:3、84:6:5:5、87:8:3:2、
84:8:4:4、82:8:5:5、80:5:5:10。
In above-mentioned Application Example and its alternative, the viscosity of anode sizing agent can also for 900cps, 950cps,
1000cps、1050cps、1100cps、1150cps、1250cps、1300cps、1350cps、1400cps、1450cps、
1500cps。
In above-mentioned Application Example and its alternative, the specification of positive and negative electrode pole piece can also for 50mm*70mm,
50mm*75mm、50mm*80mm、55mm*70mm、55mm*80mm、60mm*70mm、60mm*75mm、60mm*80mm。
In view of the present invention program embodiment is numerous, each embodiment experimental data is huge numerous, is not suitable for arranging one by one herein
Explanation is lifted, but the content of checking required for each embodiment and the final conclusion for obtaining are approached.So herein not to each reality
The checking content for applying example illustrated one by one, only using embodiment 1-3 and Application Example 1-3 as representing explanation the present patent application
Excellent part.
Specific embodiment described herein is only to the spiritual explanation for example of the present invention.Technology neck belonging to of the invention
The technical staff in domain can be made various modifications or supplement to described specific embodiment or be substituted using similar mode, but simultaneously
Do not deviate by spirit of the invention or surmount scope defined in appended claims.
It is skilled to this area although having made a detailed description and being cited some specific embodiments to the present invention
For technical staff, as long as it is obvious that can be made various changes without departing from the spirit and scope of the present invention or corrected.
Claims (8)
1. a kind of lithium-ion capacitor electrolyte, it is characterised in that the electrolyte with lithium salts and has with carbonic ester as solvent
Machine salt is solute, and lithium salts and organic salt molar concentration in the electrolytic solution are 1.6-2.0M.
2. a kind of lithium-ion capacitor electrolyte according to claim 1, it is characterised in that the carbonic ester is poly- carbon
At least one in acid esters, diethyl carbonate, methyl ethyl carbonate, dimethyl carbonate, ethylene carbonate, vinylene carbonate.
3. a kind of lithium-ion capacitor electrolyte according to claim 2, it is characterised in that the carbonic ester is by quality
Percentage is ethylene carbonate, the methyl ethyl carbonate of 35-44wt%, the dimethyl carbonate of 10-25wt%, the 1- of 35-44wt%
The vinylene carbonate composition of 2wt%.
4. a kind of lithium-ion capacitor electrolyte according to claim 1, it is characterised in that the lithium salts is LiPF6、
LiBF4、LiClO4In at least one.
5. a kind of lithium-ion capacitor electrolyte according to claim 1, it is characterised in that the organic salt is SBP-
BF4、TEA-BF4、TEMA-BF4In at least one.
6. according to a kind of any described lithium-ion capacitor electrolyte of claim 1-5, it is characterised in that the electrolyte
Preparation method be：Lithium salts is added to after being well mixed in carbonate solvent adds organic salt to be well mixed, and is configured to electrolysis
Liquid.
7. a kind of lithium-ion capacitor electrolyte according to claim 6, it is characterised in that the preparation of the electrolyte
Process is less than in the environment of 0.1ppm less than 1ppm, oxygen content in moisture and carries out.
8. a kind of lithium-ion capacitor electrolyte according to claim 6, it is characterised in that in the preparation process
The temperature of electrolyte is 40-60 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107732313A (en) * | 2017-10-27 | 2018-02-23 | 桑顿新能源科技有限公司 | A kind of long circulating high security manganese systems low cost battery core preparation method |
| CN108232302A (en) * | 2017-12-30 | 2018-06-29 | 国联汽车动力电池研究院有限责任公司 | A kind of high concentration lithium salt electrolyte suitable for silicon-based anode lithium ion battery |
| CN110085450A (en) * | 2019-04-08 | 2019-08-02 | 宁波中车新能源科技有限公司 | A kind of lithium-ion capacitor electrolyte |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107732313A (en) * | 2017-10-27 | 2018-02-23 | 桑顿新能源科技有限公司 | A kind of long circulating high security manganese systems low cost battery core preparation method |
| CN108232302A (en) * | 2017-12-30 | 2018-06-29 | 国联汽车动力电池研究院有限责任公司 | A kind of high concentration lithium salt electrolyte suitable for silicon-based anode lithium ion battery |
| CN110085450A (en) * | 2019-04-08 | 2019-08-02 | 宁波中车新能源科技有限公司 | A kind of lithium-ion capacitor electrolyte |
| CN110085450B (en) * | 2019-04-08 | 2021-02-23 | 宁波中车新能源科技有限公司 | Electrolyte for lithium ion capacitor |
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Application publication date: 20170613 |