CN106848405A - A kind of LiMn2O4/lithium titanate battery of electrolyte for lithium cells and its composition containing plumper - Google Patents
A kind of LiMn2O4/lithium titanate battery of electrolyte for lithium cells and its composition containing plumper Download PDFInfo
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- CN106848405A CN106848405A CN201710112959.8A CN201710112959A CN106848405A CN 106848405 A CN106848405 A CN 106848405A CN 201710112959 A CN201710112959 A CN 201710112959A CN 106848405 A CN106848405 A CN 106848405A
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- plumper
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- lithium titanate
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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
- H01M10/0567—Liquid materials characterised by the additives
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- H01M10/0569—Liquid materials characterised by the solvents
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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 electrolyte for lithium cells containing plumper and LiMn2O4/lithium titanate battery.It is characterized in that：The component of electrolyte for lithium cells is the electrolyte lithium salt of 1 1.5mol/L, and weight/mass percentage composition is 0.1 10% plumper, and weight/mass percentage composition is 1% 3% film for additive, and weight/mass percentage composition is 1% 5% fire retardant, balance of solvent.The electrolyte can effectively suppress the aerogenesis problem of lithium manganate material dissolving at high temperature and lithium titanate material.LiMn2O4/lithium titanate battery is prepared from by above-mentioned containing above-mentioned plumper electrolyte.LiMn2O4/lithium titanate battery of the invention has excellent chemical property, cyclical stability and security, is expected to be used widely in new-energy automobile and field of power tools.
Description
Technical field
The present invention relates to a kind of electrolyte for lithium cells containing plumper and LiMn2O4/lithium titanate battery, belong to lithium ion
Cell art.
Background technology
With the development of science and technology electronic product, electric tool, mobile product more and more appear in the life of people
In.The fast development of these products needs high performance battery.Wherein lithium ion battery is relative to lead-acid accumulator, NI-G electricity
Pond, Ni-MH battery have the advantages that operating voltage high, specific energy high, therefore obtain a wide range of applications.
The LiMn of spinel structure2O4With operating voltage (3.9V Vs Li/Li high+), it is cheap, it is environment-friendly,
It is the very promising anode material for lithium-ion batteries of a class.But the chemical property of LiMn2O4/lithium titanate battery is simultaneously unstable.By
Positive electrode LiMn in battery2O4On chemical property, cyclical stability is poor, and (55 DEG C of ＞) is used especially at high temperature
Capacity attenuation is more serious, so as to limit its commercial applications.Research shows, LiMn2O4Hot conditions under cyclic process
In, Mn2+Dissolution can accelerate, cause LiMn2O4The high temperature circulation decay of battery is very fast.Mn2+Dissolving be acid induce, electrolysis
The dissolving of manganese, mainly includes caused by HF meetings in liquid：A small amount of HF impurity that electrolyte containing F itself contains, solvent are aoxidized
The HF that the proton of generation is formed with F chemical combination, and the water of moisture impurity or the electrode material absorption in electrolyte causes electrolyte
Decompose the HF for producing.Wherein electrolyte LiPF6The HF produced when water is met is the main cause for causing manganese dissolution.
Lithium titanate (Li4Ti5O12) has spinel structure, is the negative material of a kind of " zero strain ", and discharge voltage is put down
Surely, material source is wide, clean environment firendly.Using lithium titanate as negative pole battery, with excellent cycle life.Lithium titanate material
The battery of preparation in cyclic process, especially at high temperature, battery can aerogenesis to a certain extent, cause cell expansion, influence
It is used.Its reason be lithium titanate in embedding lithium state with stronger reproducibility.Using lithium titanate as anode active material
Lithium ion battery, usually using the electrolyte close with the battery with graphite as anode, such as application number
200810052728.3 Chinese patent, the lithium ion battery with lithium titanate as anode, the solute of its electrolyte is hexafluorophosphoric acid
Lithium, solvent is the multicomponent mixture of vinyl carbonate, dimethyl carbonate and ethyl methyl carbonate.And result of study shows,
The solvent of battery electrolyte is easy to reduction reaction on metatitanic acid lithium electrode, is especially reacted in high temperature and become apparent from.
In terms of the performance and stability of lithium ion battery, electrolyte occupy center always.Current battery bound pair is new
Type lithium salts and solvent are continued in depth to study, it is proposed that many methods for improving battery performance and security, and additive
But electrolyte deficiency in some aspects can be made up, many achievements are had been achieved for.Electrolyte needs the spy with battery system
Point is adapted, therefore the design and research of electrolyte prescription have to be around different battery systems expansion.
The content of the invention
In order to improve above mentioned problem, it is an object of the invention to provide a kind of electrolyte for lithium cells containing plumper and its
LiMn2O4/the lithium titanate battery being made.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of electrolyte for lithium cells containing plumper, including following components：The electrolyte lithium salt of 1-1.5mol/L, quality
Percentage composition is the plumper of 0.1-10%, and weight/mass percentage composition is the film for additive of 1%-3%, and weight/mass percentage composition is
The fire retardant of 1%-5%, balance of solvent.
Further, described electrolyte lithium salt is that one or more in the compound with following molecular formula coexist：
LiBF4, LiPF6, LiAsF6, LiF2BC2O4。
Yet further, described plumper is pyridine or the derivative containing pyridine functional groups, such as phenylpyridine, 2- chlorine pyrroles
Pyridine, dihydropyridine etc..
Further, described film for additive is vinylene carbonate.
In addition, described fire retardant is one or more of phosphate, phosphite ester, phosphonitrile etc..
Additionally, the solvent is made up of the component of following volume ratio：Ethylene carbonate：Dimethyl carbonate：Methyl ethyl carbonate：
Propene carbonate=20-40:40-60:10-20:1-10.
A kind of LiMn2O4/lithium titanate battery, including the electrolyte described in positive plate, negative plate, barrier film and claim 1,
The positive plate is made up of the component of following mass percent：The positive active material of 88-93%, the binding agent of 2-5%, 2-
8% conductive agent；The negative plate is made up of the component of following mass percent：The negative electrode active material of 85-94%, 2-6%
Binding agent, the conductive agent of 1-10%.
Further, the positive active material be LiMn2O4 or LiMn2O4 and nickel-cobalt lithium manganate material mixture or
The mixture of LiMn2O4 and cobalt acid lithium material.
Yet further, the negative electrode active material is the mixture or metatitanic acid of lithium titanate or lithium titanate and native graphite
The mixture or lithium titanate and MCMB mixture of lithium and Delanium.
Wherein, barrier film is barrier film commonly used in the art, such as individual layer PP films, individual layer PE films or three layers of PP/PE/PP films；It is described
Conductive agent is KS-6, SP or VGCF.The binding agent is binding agent commonly used in the art, such as Kynoar PVDF, carboxymethyl
Sodium cellulosate CMC and styrene butadiene rubber sbr；In order to give full play to the capacity of the capacity of positive electrode, the negative plate and positive plate
Than being 1:1.02-1.15.Specifically, area of the area of negative plate more than positive plate, so that negative plate can be made by positive plate lid
Firmly.
The present invention compared with prior art, with advantages below and beneficial effect：
Electrolyte for lithium cells of the invention, using multi-solvents and multiple additives, the ion that improve electrolyte is led
Electrically, there is preferable compatibility with LiMn2O4, lithium titanate material, in the electrolyte as LiMn2O4/lithium titanate battery, energy
Enough suppress dissolving and the lithium titanate material high temperature aerogenesis problem of lithium manganate material, so as to improve the height of LiMn2O4/lithium titanate battery
Warm charge-discharge performance and security performance.
Brief description of the drawings
Fig. 1 is LiMn2O4/lithium titanate battery internal structure schematic diagram in embodiment 1.
Fig. 2 is the high temperature cyclic performance collection of illustrative plates of LiMn2O4/lithium titanate battery in embodiment 1.
Specific embodiment
With reference to embodiment, the invention will be further described, and embodiments of the present invention include but is not limited to following reality
Apply example.
Embodiment 1
A kind of electrolyte for lithium cells containing plumper of the present embodiment, including following components：The electrolyte of 1.3mol/L
Lithium salts LiPF6, weight/mass percentage composition is 4% plumper pyridine, and weight/mass percentage composition is 1.5% film for additive carbonic acid Asia
Vinyl acetate, weight/mass percentage composition is 3% fire retardant phosphate, balance of solvent, the solvent by following volume ratio component
Composition：Ethylene carbonate：Dimethyl carbonate：Methyl ethyl carbonate：Propene carbonate=30:50:15:5.
LiMn2O4/the lithium titanate battery of the present embodiment, as shown in figure 1, including positive plate, negative plate, electrolyte and barrier film,
Positive plate by 92% positive active material LiMn2O4,3.5% binding agent Kynoar, 4.5% conductive agent VGCF and
The mixture composition of SP.Negative plate by 94% negative electrode active material lithium titanate, 3% Kynoar, 3% conductive agent
SP.Electrolyte is above-mentioned electrolyte.Barrier film is three layers of PP/PE/PP films.The negative plate is 1 with the Capacity Ratio of positive plate:
1.05。
Fig. 2 gives the high temperature cyclic performance figure of LiMn2O4/lithium titanate battery in the present embodiment.Method of testing is：Place
Make charge and discharge cycles test in insulating box.Calorstat temperature keeps 55 DEG C, charge and discharge cycles voltage range 2.8-1.6V, charge and discharge
Electric current is 10A, and the time of repose that discharge and recharge is changed is 10 minutes.Resulting battery capacity attenuation curve is as shown in Figure 2：Institute
The LiMn2O4 prepared/lithium titanate battery high temperature circulation stability is significantly improved.
Embodiment 2
A kind of electrolyte for lithium cells containing plumper of the present embodiment, including following components：The electrolyte of 1.5mol/L
Lithium salts LiF2BC2O4, weight/mass percentage composition is 2% plumper 2- chloropyridines, and weight/mass percentage composition is 3% film for additive
Vinylene carbonate, weight/mass percentage composition is 5% fire retardant phosphate, balance of solvent, and the solvent is by following volume ratio
Component composition：Ethylene carbonate：Dimethyl carbonate：Methyl ethyl carbonate：Propene carbonate=40:40:15:5.
LiMn2O4/the lithium titanate battery of the present embodiment, including positive plate, negative plate, electrolyte and barrier film, positive plate by
93% positive active material LiMn2O4,3.5% binding agent Kynoar, 3.5% conductive agent VGCF and KS-6 it is mixed
Compound is constituted.Negative plate by 90% negative electrode active material lithium titanate and the mixture of Delanium, 6% binding agent CMC and
SBR, 4% conductive agent SP.Electrolyte is above-mentioned electrolyte.Barrier film is individual layer PP films.The appearance of the negative plate and positive plate
Amount is than being 1:1.15.
Embodiment 3
A kind of electrolyte for lithium cells containing plumper of the present embodiment, including following components：The electrolyte lithium of 1mol/L
Salt LiBF4, weight/mass percentage composition is 10% plumper phenylpyridine, and weight/mass percentage composition is 1% film for additive carbonic acid
Vinylene, weight/mass percentage composition is 1% fire retardant phosphate, balance of solvent, the solvent by following volume ratio group
It is grouped into：Ethylene carbonate：Dimethyl carbonate：Methyl ethyl carbonate：Propene carbonate=20:60:15:5.
LiMn2O4/the lithium titanate battery of the present embodiment, including positive plate, negative plate, electrolyte and barrier film, positive plate by
88% positive active material LiMn2O4 and the mixture of nickle cobalt lithium manganate, 4% binding agent Kynoar, 8% conduction
The mixture composition of agent VGCF and KS-6.Negative electrode active material lithium titanate, 6% binding agent PVDF, 9% of the negative plate by 85%
Conductive agent SP.Electrolyte is above-mentioned electrolyte.Barrier film is individual layer PP films.The negative plate is 1 with the Capacity Ratio of positive plate:
1.02。
Embodiment 4
A kind of electrolyte for lithium cells containing plumper of the present embodiment, including following components：The electrolyte of 1.5mol/L
Lithium salts LiPF6, weight/mass percentage composition is 10% plumper pyridine, and weight/mass percentage composition is 3% film for additive carbonic acid Asia
Vinyl acetate, weight/mass percentage composition is 5% fire retardant phosphate, balance of solvent, the solvent by following volume ratio component
Composition：Ethylene carbonate：Dimethyl carbonate：Methyl ethyl carbonate：Propene carbonate=30:49:20:1.
LiMn2O4/the lithium titanate battery of the present embodiment, including positive plate, negative plate, electrolyte and barrier film, positive plate by
93% positive active material LiMn2O4,3.5% binding agent Kynoar, 3.5% conductive agent VGCF and KS-6 it is mixed
Compound is constituted.Negative plate by 90% negative electrode active material lithium titanate and MCMB, 6% binding agent CMC and SBR,
4% conductive agent SP.Electrolyte is above-mentioned electrolyte.Barrier film is individual layer PE films.The Capacity Ratio of the negative plate and positive plate
It is 1:1.15.
Embodiment 5
A kind of electrolyte for lithium cells containing plumper of the present embodiment, including following components：The electrolyte lithium of 1mol/L
Salt LiAsF6, weight/mass percentage composition is 0.1% plumper 2- chloropyridines, and weight/mass percentage composition is 2% film for additive carbon
Sour vinylene, weight/mass percentage composition is 2.5% fire retardant phosphate, balance of solvent, and the solvent is by following volume ratio
Component composition：Ethylene carbonate：Dimethyl carbonate：Methyl ethyl carbonate：Propene carbonate=35:45:10:10.
LiMn2O4/the lithium titanate battery of the present embodiment, including positive plate, negative plate, electrolyte and barrier film, positive plate by
93% positive active material LiMn2O4,3.5% binding agent Kynoar, 3.5% conductive agent VGCF and KS-6 it is mixed
Compound is constituted.Negative plate by 90% negative electrode active material lithium titanate, 6% binding agent Kynoar, 4% conductive agent
SP.Electrolyte is above-mentioned electrolyte.Barrier film is individual layer PP films.The negative plate is 1 with the Capacity Ratio of positive plate:1.06.
According to above-described embodiment, the present invention just can be well realized.
Claims (9)
1. a kind of electrolyte for lithium cells containing plumper, it is characterised in that including following components：The electrolyte of 1-1.5mol/L
Lithium salts, weight/mass percentage composition is the plumper of 0.1-10%, and weight/mass percentage composition is the film for additive of 1%-3%, quality hundred
Content is divided to be the fire retardant of 1%-5%, balance of solvent.
2. a kind of electrolyte for lithium cells containing plumper according to claim 1, it is characterised in that described electrolyte
Lithium salts is that one or more in the compound with following molecular formula coexist：LiBF4, LiPF6, LiAsF6, LiF2BC2O4。
3. a kind of electrolyte for lithium cells containing plumper according to claim 1, it is characterised in that described plumper
For pyridine or the derivative containing pyridine functional groups.
4. a kind of electrolyte for lithium cells containing plumper according to claim 1, it is characterised in that described film forming adds
Plus agent is vinylene carbonate.
5. a kind of electrolyte for lithium cells containing plumper according to claim 1, it is characterised in that described fire retardant
It is one or more in phosphate, phosphite ester, phosphonitrile.
6. a kind of electrolyte for lithium cells containing plumper according to claim 1, it is characterised in that the solvent is by such as
Lower volume than component constitute：Ethylene carbonate：Dimethyl carbonate：Methyl ethyl carbonate：Propene carbonate=20-40:40-60:
10-20:1-10。
7. a kind of LiMn2O4/lithium titanate battery, it is characterised in that including described in positive plate, negative plate, barrier film and claim 1
Electrolyte, the positive plate is made up of the component of following mass percent：The positive active material of 88-93%, 2-5% it is viscous
Knot agent, the conductive agent of 2-8%；The negative plate is made up of the component of following mass percent：The negative electrode active material of 85-94%
Matter, the binding agent of 2-6%, the conductive agent of 1-10%.
8. a kind of LiMn2O4/lithium titanate battery according to claim 7, it is characterised in that the positive active material is
The mixture of the mixture or LiMn2O4 and cobalt acid lithium material of LiMn2O4 or LiMn2O4 and nickel-cobalt lithium manganate material.
9. a kind of LiMn2O4/lithium titanate battery according to claim 7, it is characterised in that the negative electrode active material is
The mixture or lithium titanate and interphase of the mixture or lithium titanate and Delanium of lithium titanate or lithium titanate and native graphite
Carbon microspheres mixture.
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| CN201710112959.8A CN106848405A (en) | 2017-02-28 | 2017-02-28 | A kind of LiMn2O4/lithium titanate battery of electrolyte for lithium cells and its composition containing plumper |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107887644A (en) * | 2017-11-09 | 2018-04-06 | 安徽智森电子科技有限公司 | A kind of electrolyte of lithium battery |
| CN108091879A (en) * | 2017-12-18 | 2018-05-29 | 江苏双登富朗特新能源有限公司 | Highly secure lithium ion dynamic battery |
| CN115395081A (en) * | 2022-09-05 | 2022-11-25 | 江苏正力新能电池技术有限公司 | Secondary battery and power utilization device |
| WO2023205034A1 (en) * | 2022-04-18 | 2023-10-26 | Maxwell Technologies Korea Co., Ltd. | Halogenated compounds for energy storage device formulations |
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| US20020025477A1 (en) * | 2000-07-14 | 2002-02-28 | Mitsubishi Chemical Corporation | Non-aqueous electrolytic solution and secondary battery containing same |
| CN101809693A (en) * | 2007-07-25 | 2010-08-18 | 霍尼韦尔国际公司 | High voltage electrolytes |
| CN104900911A (en) * | 2015-06-02 | 2015-09-09 | 中国东方电气集团有限公司 | Lithium manganate battery electrolyte solution containing acidity removing agent |
| CN105958110A (en) * | 2016-06-14 | 2016-09-21 | 宁德新能源科技有限公司 | Electrolyte and secondary battery containing same |
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2017
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| US20020025477A1 (en) * | 2000-07-14 | 2002-02-28 | Mitsubishi Chemical Corporation | Non-aqueous electrolytic solution and secondary battery containing same |
| CN101809693A (en) * | 2007-07-25 | 2010-08-18 | 霍尼韦尔国际公司 | High voltage electrolytes |
| CN104900911A (en) * | 2015-06-02 | 2015-09-09 | 中国东方电气集团有限公司 | Lithium manganate battery electrolyte solution containing acidity removing agent |
| CN105958110A (en) * | 2016-06-14 | 2016-09-21 | 宁德新能源科技有限公司 | Electrolyte and secondary battery containing same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107887644A (en) * | 2017-11-09 | 2018-04-06 | 安徽智森电子科技有限公司 | A kind of electrolyte of lithium battery |
| CN108091879A (en) * | 2017-12-18 | 2018-05-29 | 江苏双登富朗特新能源有限公司 | Highly secure lithium ion dynamic battery |
| WO2023205034A1 (en) * | 2022-04-18 | 2023-10-26 | Maxwell Technologies Korea Co., Ltd. | Halogenated compounds for energy storage device formulations |
| CN115395081A (en) * | 2022-09-05 | 2022-11-25 | 江苏正力新能电池技术有限公司 | Secondary battery and power utilization device |
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Application publication date: 20170613 |