CN108134136A - A kind of electrolyte and a kind of secondary cell - Google Patents
A kind of electrolyte and a kind of secondary cell Download PDFInfo
- Publication number
- CN108134136A CN108134136A CN201711462727.1A CN201711462727A CN108134136A CN 108134136 A CN108134136 A CN 108134136A CN 201711462727 A CN201711462727 A CN 201711462727A CN 108134136 A CN108134136 A CN 108134136A
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- lithium ion
- ion battery
- bmi
- mmds
- 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
Classifications
-
- 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
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
Abstract
The invention discloses a kind of electrolyte and a kind of secondary cell,In the electrolytic solution simultaneously added with N,N'‑(4,4' methylenediphenyls) bismaleimide (BMI) and methane-disulfonic acid methylene ester (MMDS),The electrolyte is applied to each may participate in film forming in anode in lithium ion battery,Functional additive package MMDS and BMI synergistic effects in the present invention,Have both the toughness of polymer and the height of inorganic sulfosalt lead it is ionic,And the film formed after have relatively low impedance,High temperature stability performance is excellent,It is survivable under the high temperature conditions,Therefore solvent can effectively be prevented to consume lithium with reacting for anode,Applied to can be while reducing big multiplying power charging temperature and rising in lithium ion battery,Also the high temperature storage capacity retention ratio of lithium ion battery can be improved,It also is able to significantly improve room temperature cycles performance and high-temperature storage performance under lithium ion battery high-voltage simultaneously.
Description
Technical field
The present invention relates to field of batteries, more particularly, to a kind of electrolyte and a kind of secondary cell.
Background technology
Lithium ion battery because have many advantages, such as it is higher than energy, have extended cycle life, self discharge it is small, be widely used in consumer
In electronic product and energy storage and power battery.In consumer electronics product field, there is the lithium battery of rapid charge characteristic
The mainstream product in the market is increasingly becoming, Fast Charge Battery (abbreviation quick charging battery) is mainly charged by big multiplying power and realized at present, greatly
Multiplying power is easy to charge to cause internal temperature of battery quickly to increase, and deteriorates battery.In addition to this, battery is in storing process
In, particularly under hot conditions, the capacitance loss of inside battery is more serious, and end product usage time is caused to shorten.Thus may be used
See, the Wen Sheng and high temperature storage capacity retention ratio for improving quick charging battery battery become particularly important.
The charging Wen Sheng and high temperature storage capacity retention ratio of lithium ion battery are influenced by factors, wherein, electrolysis
Important component of the liquid as lithium ion battery, having on its performance gravely influences.Therefore, there is an urgent need for a kind of performance is excellent now
While big multiplying power charging temperature liter is reduced, the high temperature storage capacity that can also improve lithium ion battery is kept different electrolyte
Rate.
Invention content
In view of the drawbacks of the prior art, the technical problems to be solved by the invention are to provide a kind of electrolyte and one kind is secondary
Battery.
The technical solution used in the present invention is：
The present invention provides a kind of electrolyte, and comprising solvent, electrolyte and additive, the additive contains N, N'- (4,
4'- methylenediphenyls) bismaleimide and methane-disulfonic acid methylene ester.
Preferably, the mass fraction of the N, N'- (4,4'- methylenediphenyl) bismaleimide in the electrolytic solution is
0.05%~3%.
Further, the mass fraction of the N, N'- (4,4'- methylenediphenyl) bismaleimide in the electrolytic solution
It is 0.1%~2%.
Preferably, the mass fraction of the methane-disulfonic acid methylene ester in the electrolytic solution is 0.01%~10%.
Further, the mass fraction of the methane-disulfonic acid methylene ester in the electrolytic solution is 0.1~3%.
Preferably, the solvent is non-aqueous solvent.
The present invention also provides a kind of secondary cell, comprising negative plate, also comprising above-described electrolyte.
Preferably, the negative plate is graphite cathode piece.
The beneficial effects of the invention are as follows：
N, N'- (4,4'- methylenediphenyls) bismaleimide (BMI) and first are included in electrolyte provided by the invention
Alkane disulfonic acid methylene ester (MMDS) can also can applied in lithium ion battery while big multiplying power charging temperature liter is reduced
The high temperature storage capacity retention ratio of lithium ion battery is improved, while also is able to significantly improve the room under lithium ion battery high-voltage
Warm cycle performance and high-temperature storage performance.Compared to independent addition BMI or MMDS, since the oxidizing potential of MMDS and BMI omits
Film forming is each may participate in less than the oxidizing potential of solvent, therefore in anode, the functional additive package MMDS and BMI in the present invention
Synergistic effect, it is mainly Li to participate in the film component to be formed2SO3And ROSO2Li and BMI ring-opening polymerisations form, which has both polymer
Toughness and inorganic sulfosalt height lead it is ionic, and the film formed after there is relatively low impedance, high temperature stability performance is excellent, in height
It is survivable under the conditions of temperature, therefore solvent can effectively be prevented to consume lithium with reacting for anode；Secondly combined additive MMDS and
BMI can reduce initial anode interface impedance and improve anode interface high-temperature stability, therefore can effectively reduce quick charge temperature
It rises and high temperature storage capacity retention ratio；In addition combined additive MMDS and BMI has good compatibility, and energy with graphite cathode
The protective film for stablizing densification is formed in anode, so as to improve the chemical property of battery.
Specific embodiment
The technique effect of design and the generation of the present invention is clearly and completely described below with reference to embodiment, with
It is completely understood by the purpose of the present invention, feature and effect.Obviously, described embodiment is that the part of the present invention is implemented
Example rather than whole embodiments, based on the embodiment of the present invention, those skilled in the art is not before making the creative labor
Obtained other embodiment is put, belongs to the scope of protection of the invention.
Embodiment 1：The preparation of electrolyte L1#~L12#
It is EC in mass ratio:DEC:PC:FEC=30:50:15:5 uniform mixing EC, DEC, PC and FEC form organic molten
Agent takes fully dry lithium salts LiPF6It is dissolved in above-mentioned organic solvent, obtains a concentration of 1mol/L of lithium salts, then add in
Combined additive BMI and MMDS are uniformly mixed, obtain electrolyte.The structural formula of the BMI is：The structural formula of the MMDS is:
The component relationship of combined additive is as shown in table 1 in electrolyte L1#~L12#.
Table 1
Embodiment 2：The preparation of lithium ion battery B1#~B12#
(1) preparation of positive plate：By cobalt acid lithium (LiCoO2), binding agent (Kynoar), conductive agent (acetylene black) press
It is LiCoO according to weight ratio2: Kynoar: acetylene black=96: mixed at 2: 2 add in N-Methyl pyrrolidone (NMP),
The lower stirring of de-airing mixer effect obtains anode sizing agent to system into uniform shape；Anode sizing agent is evenly applied to thickness as 12 μ
On the aluminium foil of m；Aluminium foil after room temperature is dried is transferred to 120 DEG C of oven drying 1h, then obtains anode by cold pressing, cutting
Piece.
(2) preparation of negative plate：By graphite, acetylene black, thickener sodium carboxymethylcellulose (CMC), binding agent butylbenzene rubber
Glue is graphite: acetylene black: binding agent butadiene-styrene rubber: thickener sodium carboxymethylcellulose (CMC)=95: 2: 2: 1 according to weight ratio
It is mixed, after being added to deionized water, negative electrode slurry is obtained under the stirring action of de-airing mixer stirring；By negative electrode slurry
It is coated uniformly on copper foil；Copper foil is transferred to 120 DEG C of oven drying 1h after room temperature is dried, then by being cold-pressed, cutting
To negative plate.
(3) preparation of lithium ion battery：Positive plate, lithium battery isolation membrane, negative plate are folded in order, make lithium battery every
It is between positive and negative plate from film and plays the role of isolation, then winding obtains naked battery core；Naked battery core is placed in outer packing foil
In, electrolyte L1#~L12# in embodiment 1 is injected into dried battery respectively, by Vacuum Package, standing, change
Into processes such as, shapings, obtain lithium ion battery B1#~B12#, the lithium ion battery finally obtained can be applied to 4.4V and more than
Voltage regime.
Embodiment 3：The cycle performance test of lithium ion battery B1#~B12#
Lithium ion battery B1#~B12# in Example 2 is tested as follows：At 25 DEG C, by lithium from
Sub- battery is with 1C constant-current charges to 4.4V, and then constant-voltage charge to electric current is 0.05C, then with 1C constant-current discharges to 3.0V, at this time
To recycle for the first time, carry out 100 times, 300 times, 500 cycle charging/electric discharges respectively according to above-mentioned cycling condition, calculate respectively
Go out circulating battery 100 times, 300 times, 500 times cycle after capacity retention ratio, wherein, the capacity retention ratio after cycle is according to the following formula
Calculated, the capacity retention ratio after cycle=(discharge capacity after corresponding cycle-index/discharge capacity recycled for the first time) ×
100%, each lithium ion battery after tested obtained relevant test data referring to table 2.
Table 2
From the related data in table 2 it is known that compared to being not added with BMI and MMDS and individually adding single component
The lithium ion battery of (BMI or MMDS) is compared, and the lithium ion battery that combined additive BMI and MMDS are added while of the invention exists
After 100 times, 300 times, 500 cycles, still there is higher capacity retention ratio, the experimental results showed that will simultaneously containing BMI and
The electrolyte of MMDS is added to the cycle performance that lithium ion battery can be improved in lithium ion battery, is particular enable to improve lithium ion
Cycle performance of the battery under the high voltage of more than 4.4V.
Embodiment 4：Thermostability test after lithium ion battery B1#~B12# cycles
Lithium ion battery B1#~B12# in Example 3 after 500 loop tests is surveyed as follows
Examination：It is at 25 DEG C with 0.5C electric current constant-current charges to 4.4V, then using 4.4V constant-voltage charges to electric current as 0.025C
Then battery is placed in 150 DEG C of high temperature furnace and is kept for 1 hour by 4.4V fully charged states, the state of battery, battery after observation test
Not on fire not explode as passing through, 10 batteries of every group of test, percent of pass result is shown in Table 3.
Table 3
From the related data in above-mentioned table 3 it is known that the lithium ion battery for adding BMI and MMDS in the present invention simultaneously follows
Preferable thermal stability is respectively provided with after ring, the results showed that the electrolyte simultaneously containing BMI and MMDS is applied in lithium ion battery
Afterwards, the high-temperature storage performance after lithium ion battery cycle can be improved.
Embodiment 5：The charging temperature of lithium ion battery B1#~B12# rises test
Lithium ion battery B1#~B12# in Example 2 is tested as follows：At 25 DEG C, by battery with
0.5C constant-current discharges are to 3.0V, then with constant pressure after different rate of charge 1,1.5,2,3,5C constant-current charges to 4.4V to electric current
It for 0.05C, so recycles, until each rate of charge is completed, battery surface center is tested by multichannel temperature logger
Temperature, and record.Record to obtain maximum temperature such as the following table 4 under each rate of charge, unit for DEG C.
Table 4
From the data in above-mentioned table 4 it is known that compared to being not added with BMI and MMDS and individually adding single component
Lithium ion battery, at the same add BMI and MMDS to lithium ion battery charging Wen Shengjun have different degrees of improvement, show to contain simultaneously
After the electrolyte for having BMI and MMDS is applied in lithium ion battery, the charging temperature rise model of lithium ion battery can be improved.
Embodiment 6：The capacity retention ratio of lithium ion battery B1#~B12# storages 30 days at 60 DEG C
Lithium ion battery B1#~B12# in Example 2 is tested as follows：With 0.5C electric currents at 25 DEG C
Constant-current charge is discharged to 3.0V to 4.4V, then using 4.4V constant-voltage charges to electric current as 0.05C with 0.5C, records the discharge capacity
For initial battery capacity.It is made to 4.4V, then using 4.4V constant-voltage charges to electric current as 0.05C with 0.5C electric current constant-current charges again
In 4.4V fully charged states, then battery is placed in 60 DEG C of insulating box and is kept for 30 days.Battery is taken out after 30 days, is put with 0.5C
Electricity records the discharge capacity as the capacity after 60 DEG C of storages 30 days, and with 0.5C electric current constant-current charges to 4.4V to 3.0V, then with
4.4V constant-voltage charges to electric current is 0.05C, and 3.0V is discharged to 0.5C, records the discharge capacity as battery recovery capacity, specifically
Shown in experimental result table 5.
Table 5
From the data in table 5 it is known that the lithium ion battery simultaneously added with BMI and MMDS stores 30 days at 60 DEG C
Capacity retention ratio significantly gets a promotion, the experimental results showed that the electrolyte simultaneously containing BMI and MMDS is applied to lithium ion battery
In after, the high temperature storage capacity retention ratio of lithium ion battery can be improved.
Embodiment 7
It is EC in mass ratio:DEC:PC:FEC=30:50:15:5 uniform mixing EC, DEC, PC and FEC form organic molten
Agent takes fully dry lithium salts LiPF6It is dissolved in above-mentioned organic solvent, obtains a concentration of 1mol/L of lithium salts, then add in
Combined additive BMI and MMDS, the mass fractions of the BMI in the electrolytic solution are 0.05%, and the MMDS is in the electrolytic solution
Mass fraction is 10%, is uniformly mixed, obtains electrolyte.
Embodiment 8
It is EC in mass ratio:DEC:PC:FEC=30:50:15:5 uniform mixing EC, DEC, PC and FEC form organic molten
Agent takes fully dry lithium salts LiPF6It is dissolved in above-mentioned organic solvent, obtains a concentration of 1mol/L of lithium salts, then add in
Combined additive BMI and MMDS, the mass fractions of the BMI in the electrolytic solution are 1.5%, the matter of the MMDS in the electrolytic solution
It is 0.01% to measure score, is uniformly mixed, obtains electrolyte.
Claims (8)
1. a kind of electrolyte includes solvent, electrolyte and additive, which is characterized in that the additive contains N, N'- (4,4'-
Methylenediphenyl) bismaleimide and methane-disulfonic acid methylene ester.
2. electrolyte according to claim 1, which is characterized in that the N, N'- (4,4'- methylenediphenyl) span comes
The mass fraction of acid imide in the electrolytic solution is 0.05%~3%.
3. electrolyte according to claim 2, which is characterized in that the N, N'- (4,4'- methylenediphenyl) span comes
The mass fraction of acid imide in the electrolytic solution is 0.1%~2%.
4. according to claim 1-3 any one of them electrolyte, which is characterized in that the methane-disulfonic acid methylene ester is being electrolysed
Mass fraction in liquid is 0.01%~10%.
5. electrolyte according to claim 4, which is characterized in that the matter of the methane-disulfonic acid methylene ester in the electrolytic solution
It is 0.1~3% to measure score.
6. according to claim 1-3,5 any one of them electrolyte, which is characterized in that the solvent is non-aqueous solvent.
7. a kind of secondary cell, includes negative plate, which is characterized in that also comprising claim 1-6 any one of them electrolyte.
8. secondary cell according to claim 7, which is characterized in that the negative plate is graphite cathode piece.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711462727.1A CN108134136B (en) | 2017-12-28 | 2017-12-28 | Electrolyte and secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711462727.1A CN108134136B (en) | 2017-12-28 | 2017-12-28 | Electrolyte and secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108134136A true CN108134136A (en) | 2018-06-08 |
| CN108134136B CN108134136B (en) | 2020-12-01 |
Family
ID=62393724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711462727.1A Active CN108134136B (en) | 2017-12-28 | 2017-12-28 | Electrolyte and secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108134136B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109860708A (en) * | 2019-01-04 | 2019-06-07 | 上海德朗能动力电池有限公司 | A kind of lithium titanate battery electrolyte |
| CN112448035A (en) * | 2020-11-25 | 2021-03-05 | 东莞市天丰电源材料有限公司 | High-voltage lithium ion battery electrolyte and preparation method thereof |
| CN116799308A (en) * | 2023-08-25 | 2023-09-22 | 深圳华驰新能源科技有限公司 | Lithium ion battery and electrolyte thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120214048A1 (en) * | 2011-02-22 | 2012-08-23 | National Taiwan University Of Science And Technology | Lithium battery and method for fabricating the same |
| CN106170886A (en) * | 2014-04-03 | 2016-11-30 | 3M创新有限公司 | Additive agent electrolyte for lithium ion battery |
| JP2016213103A (en) * | 2015-05-12 | 2016-12-15 | Ｎｅｃエナジーデバイス株式会社 | Lithium ion secondary battery and method for manufacturing the same |
| CN107210486A (en) * | 2015-01-30 | 2017-09-26 | 三菱化学株式会社 | Non-aqueous electrolyte and the nonaqueous electrolyte secondary battery using the electrolyte |
| CN107204485A (en) * | 2017-03-31 | 2017-09-26 | 宁波中车新能源科技有限公司 | A kind of battery capacitor polynary electrolyte of low temperature |
-
2017
- 2017-12-28 CN CN201711462727.1A patent/CN108134136B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120214048A1 (en) * | 2011-02-22 | 2012-08-23 | National Taiwan University Of Science And Technology | Lithium battery and method for fabricating the same |
| CN106170886A (en) * | 2014-04-03 | 2016-11-30 | 3M创新有限公司 | Additive agent electrolyte for lithium ion battery |
| CN107210486A (en) * | 2015-01-30 | 2017-09-26 | 三菱化学株式会社 | Non-aqueous electrolyte and the nonaqueous electrolyte secondary battery using the electrolyte |
| JP2016213103A (en) * | 2015-05-12 | 2016-12-15 | Ｎｅｃエナジーデバイス株式会社 | Lithium ion secondary battery and method for manufacturing the same |
| CN107204485A (en) * | 2017-03-31 | 2017-09-26 | 宁波中车新能源科技有限公司 | A kind of battery capacitor polynary electrolyte of low temperature |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109860708A (en) * | 2019-01-04 | 2019-06-07 | 上海德朗能动力电池有限公司 | A kind of lithium titanate battery electrolyte |
| CN112448035A (en) * | 2020-11-25 | 2021-03-05 | 东莞市天丰电源材料有限公司 | High-voltage lithium ion battery electrolyte and preparation method thereof |
| CN116799308A (en) * | 2023-08-25 | 2023-09-22 | 深圳华驰新能源科技有限公司 | Lithium ion battery and electrolyte thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108134136B (en) | 2020-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103779607B (en) | A kind of electrolyte and lithium rechargeable battery | |
| CN111769329B (en) | Lithium ion battery | |
| CN105655640B (en) | A kind of nonaqueous electrolytic solution and the lithium ion battery containing the electrolyte | |
| CN104810550A (en) | Preparation method of functional additive-containing lithium ion battery | |
| CN106602141B (en) | A kind of electrolyte and secondary cell | |
| CN105914399A (en) | Electrolyte and lithium-ion cell containing same | |
| CN106602129B (en) | A kind of polyion battery and preparation method thereof | |
| CN106410279A (en) | Electrolyte and secondary battery | |
| CN105895957B (en) | Battery fluid and lithium ion battery | |
| WO2018099097A1 (en) | Electrolyte and secondary lithium battery | |
| CN102610790B (en) | Lithium rechargeable battery and its positive plate | |
| CN104916867A (en) | Electrolyte and lithium ion battery containing electrolyte | |
| CN105633454A (en) | High-voltage and wide-temperature amplitude polymer lithium battery for 3C digital camera and fabrication method of polymer lithium battery | |
| CN108987808A (en) | A kind of high-voltage lithium ion batteries nonaqueous electrolytic solution and lithium ion battery | |
| CN105789611A (en) | Electrolyte of considering high temperature cycle performance and low temperature cycle performance of battery and lithium-ion battery | |
| CN103346350A (en) | Electrolyte for improving performance of lithium ion battery and battery | |
| CN104466098A (en) | Ionic-liquid-coated lithium ion battery positive plate as well as preparation method thereof and lithium ion battery | |
| CN108987802B (en) | Non-aqueous electrolyte for high-voltage lithium ion battery | |
| CN105811009B (en) | Electrolyte and lithium ion battery comprising same | |
| CN108134136A (en) | A kind of electrolyte and a kind of secondary cell | |
| CN105762410A (en) | Non-aqueous electrolyte and lithium-ion battery using same | |
| CN107579301B (en) | Formation process of lithium iron phosphate power battery | |
| CN105489936A (en) | Non-aqueous electrolyte and lithium ion battery comprising same | |
| CN114938689A (en) | Electrochemical device and electronic device | |
| CN105489882A (en) | Positive pole piece, preparation method thereof and lithium ion battery |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |