CN1306645C - Lithium ion battery electrolyte containing organophosphorus compounds and battery formed thereby - Google Patents
Lithium ion battery electrolyte containing organophosphorus compounds and battery formed thereby Download PDFInfo
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- CN1306645C CN1306645C CNB2004100161993A CN200410016199A CN1306645C CN 1306645 C CN1306645 C CN 1306645C CN B2004100161993 A CNB2004100161993 A CN B2004100161993A CN 200410016199 A CN200410016199 A CN 200410016199A CN 1306645 C CN1306645 C CN 1306645C
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Abstract
The present invention relates to a lithium ion electrolyte containing an organic phosphorus compound and a battery formed from the lithium ion electrolyte. The present invention is characterized in that the electrolyte is formed by mixing the organic phosphorus compound with a lithium salt and carbonic ester according to any proportion, the structural formula of the organic phosphorus compound is disclosed in the formula (I), wherein R1, R2 and R3 in the structural formula can be alkyl groups C<n>H<2n+1> and alkyl groups containing halogen (Cl, Br and I), or carbon atoms in R are connected with alkanoyl substituent groups, and the number n of the carbon atoms in R is larger than or equal to 1 and smaller than or equal to 12. The battery formed from the electrolyte by using a transition metal embedded lithium compound as a positive electrode, using a carbon material as a negative electrode and using a porous polyhydrocarbon compound as a membrane has electrochemical stabilization at a range of 2.5 to 4.3V and has the characteristics of low temperature resistance, fire resistance and safety, and the discharging efficiency is greatly increased.
Description
Technical field
The present invention relates to lithium ion battery, the lithium ion battery of electrolyte and composition thereof contains organic phosphorus compound in the lithium-ion battery electrolytes that relates to or rather.Belong to the lithium ion battery field.
Background technology
Along with portable electric appts, as mobile phone, laptop computer is universal day by day, and corresponding power supply is also had higher requirement.Lithium ion battery is widely used in the mobile electronic terminal apparatus field with its in light weight, high specific energy, high open circuit voltage, long storage life, low advantages such as self-discharge rate.Since Japanese Sony company released commercial lithium ion battery in 1991 first, the lithium ion battery industry has obtained develop rapidly.Secondary lithium battery uses two kinds different can reversiblely to embed/deviate from the lithium ion compound as the both positive and negative polarity active material.Lithium intercalation compound replaces the lithium anode in the serondary lithium battery both to keep the high advantage of lithium battery operating voltage, has solved the safety problem that lithium battery causes again to a great extent, has also improved the efficiency for charge-discharge and the cycle life of battery simultaneously greatly.Commercialization lithium ion battery anode uses transition metal oxide material such as LiCoO at present
2, LiNiO
2, LiMn
2O
4, negative electrode use raw material of wood-charcoal material such as native graphite, the mutually little charcoal ball in centre (MCMB), the wherein general non-aqueous organic carbonate that is dissolved with lithium salts that uses of electrolyte.Ethylene carbonate (EC), propene carbonate (PC), gamma-butyrolacton (GBL), vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC) are present several organic solvents that are widely used in the lithium-ion battery electrolytes.Non-water organic electrolyte works move to transmit lithium ion between negative electrode and anode, and electrolyte should be stablized in the voltage range of battery operation and can transmit lithium ion fast.Electrolyte is extremely important for lithium ion battery, directly influences and determine the performance of lithium ion battery.The research and development of electrolyte also is subjected to producing the attention with researcher day by day.
At present adopt the multicomponent mixed solvent as the secondary lithium battery electrolyte solvent mostly in research of just carrying out in the laboratory and the industrial production.Single solvent often can not reach actual requirement simultaneously on performance, the multicomponent mixed solvent that obtains after multiple solvent is mixed the by a certain percentage actual requirement that then is content with very little.US Patent No.5,525,443 and 5,521,027 discloses the mixed electrolytic solution of linear carbonates, cyclic carbonate.Cyclic carbonate has bigger polarity, the lithium that can dissociate fully, but bigger viscosity has reduced the coefficient of conductivity of lithium ion.Wherein hang down the viscosity that the low viscous linear carbonates of polarity can effectively reduce the electrolyte that contains cyclic carbonate by sneaking into.Propene carbonate (PC) is as the lithium-ion battery electrolytes cosolvent, in battery charge and discharge process with Li
+Embed carbon cathode material altogether, cause material to be peeled off and cause the reduction of battery capacity decay battery cycle life.Under 37 ℃ of normal temperature of ethylene carbonate (EC) fusing point is solid-state, a large amount of cryogenic properties that can reduce battery of using.Phosphoric acid fat has the superperformance solvent, is widely used in industrial circle.Use low temperature and security performance that phosphoric acid fat can effectively improve lithium ion battery.Table 1 provides the molten point and the boiling point of several lithium ion battery solvents.The fusing point of phosphate is lower than corresponding carbonic ester.And phosphate can be used as fire retardant, can resolve into phosphoric acid or metaphosphoric acid in flame, promotes the charing of resin, thereby reaches fire-retardant effect.
Table 1
| Solvent | Fusing point M/ ℃ | Boiling point B/ ℃ |
| Propene carbonate (PC) | -49 | 240 |
| Ethylene carbonate (EC) | 40 | 248 |
| Trimethyl phosphate | -70 | 180～190 |
| Triethyl phosphate | -56 | 215 |
| Tributyl phosphate | -80 | 289 decompose |
This shows, can in electrolyte, contain phosphate, improve existing lithium-ion battery electrolytes performance, can play the hope that fire retardation has become vast battery operated person again.Thereby draw purpose of the present invention.
Summary of the invention
Defective at carbonates organic compound in the present lithium-ion battery electrolytes exists the invention provides a kind of lithium-ion battery electrolytes and lithium ion battery thereof.
A kind of lithium-ion battery electrolytes of the present invention is by containing the organic phosphorus compound shown in the formula (I), mixing by arbitrary proportion with lithium salts and other organic solvents.
In the formula, R
1, R
2And R
3Can be alkyl C
nH
2n+1, halogen-containing (Cl, Br, I) alkyl, perhaps the carbon atom among the R is connected with the heterocyclic substituting group.Carbon atom number 1≤n≤12 among the R wherein.
Described lithium salts is selected from LiClO
4, LiCF
3SO
3, LiPF
6, LiBF
4, LiAsF
6, and LiN (CF
3SO
2)
2In a kind of; That the most frequently used is LiPF
6And LiBF
4Lithium salts.
Described organic solvent is meant any class organic solvent that is applied to lithium-ion battery electrolytes, as ethylene carbonate (EC), propene carbonate (PC), gamma-butyrolacton (GBL), vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl acetate (MA), methyl propionate (MP), methyl formate (MF).This organic solvent can be a kind of, two kinds or multiple.
The compound of described organophosphor or be trimethyl phosphate, tributyl phosphate (TBP), triethyl phosphate etc.
Lithium battery of the present invention comprises: the transition metal lithium intercalation compound is made anode, and high power capacity raw material of wood-charcoal material is as negative electrode, the porous polyolefin compound as barrier film and on also contain the electrolyte of organic phosphorus compound.
The compound that formula provided by the present invention (I) contains organophosphor prepares and replaces with common methodology of organic synthesis.
In sum, the compound that contains in the lithium-ion electrolyte of organic phosphorus compound that contains provided by the invention, in the working voltage scope (2.5-4.3V) of lithium ion battery, electrochemical stability, improved existing electrolyte for lithium ion battery performance when having guaranteed lithium ion battery stable operation again, used to have low temperature resistant, flame-retarding performance.And discharging efficiency improves (seeing Table 4) greatly
Description of drawings
Fig. 1 is 1mol/L LipF
6-DMC/TBP cyclic voltammetry curve figure.Abscissa is a voltage, the V of unit: ordinate is an electric current, the mA of unit.Three circulations have been shown among the figure.
Fig. 2 is 1mol/L LipF
6-DMC/TBP cyclic voltammetry curve figure.Abscissa is a voltage, the V of unit; Ordinate is an electric current, the mA of unit.
Fig. 3 is 1mol/L LipF
6-DMC/TBP cycle performance figure.Abscissa is a cycle-index, the unit number of times; Ordinate is a specific capacity, the mAh/g of unit.
Fig. 4 is 1mol/L LipF
6-TBP/DMC electrolyte (1: 1: 1) and 1mol/L LipF
6-EC/DMC (1: 1) charging and discharging curve compares, and abscissa is specific capacity (mAh/g), and ordinate is cell voltage (V).
Fig. 5 is that the charcoal cathode pole piece is at 1mol/L LipF
6Stereoscan photograph (SEM) after+DMC/TBP circulation three times
Embodiment
Below in conjunction with example creativeness of the present invention is further illustrated, but the present invention never only is confined to embodiment.
Select other organic phosphorus compounds described in the summary of the invention for use, press the electrolyte of arbitrary proportion composition and the battery of composition thereof, all have suitable effect with described embodiment with other lithium salts and carbonate salt.
Embodiment 1: the preparation of electrolyte
By mixing DMC: EC: TBP (tributyl phosphate)=1: 1: 1 (volume ratio), and in drying box, add 1mol/LipF
6Prepare 50ml electrolyte.DMC, TBP all are Aldrich company products.Electrolyte MaxH
2O＜20ppm, MaxHF＜50ppm.
Its molecule highest occupied molecular orbital energy and molecule lowest unoccupied molecular orbital energy are respectively-6.792ev and 0.02ev as calculated, thereby show that it meets the demands aspect electrochemical stability, fusing point is-80 ℃, and 289 ℃ of no boiling points of decomposition and 25 ℃ of conductivity are that 1.92ms/cm all satisfies the requirement of lithium ion battery to electrolyte.
Embodiment 2: the preparation of electrolyte
By mixing DMC: TBP (tributyl phosphate)=1: 1 (volume ratio), and in drying box, add 1mol/L LipF
6Prepare 50ml electrolyte.DMC, TBP all are Aldric company products.Electrolyte MaxH
2O＜20ppm, MaxHF＜50ppm.
Comparative example 1: the preparation of electrolyte
By mixing EC: DMC=1: 1 (volume ratio), and in drying box, add 1mol/L LipF
6Prepare 50ml electrolyte.EC: DMC all is Aldrich company products.Electrolyte MaxH
2O＜20ppm, MaxHF＜50ppm.
Embodiment 2 and comparative example 1 described two kinds of electrolyte are placed in the thermostatic container, under-30 ℃ and 10 ℃ of temperature 4 hours respectively, the state of observation sample then.Observed result is as shown in table 2:
Table 2
| Temperature/℃ | The state of sample | |
| Embodiment 2 | -30 | Liquid |
| Comparative example 1 | -30 | Solid-state |
| Implement 2 | 10 | Liquid |
| Comparative example 1 | 10 | Liquid |
Embodiment 3
Two kinds of electrolyte of use embodiment 2 and comparative example 1 are dressed up the button cell of φ 20 respectively, and as negative pole, the Li sheet is as positive pole to use carbon activity material (Osaka gas Company MCMB-10-28).Test the performance of electrolyte at normal temperatures.Test result is as shown in table 3.Charging current 0.2mA/cm
2, experimental result shows that TBP can be used as the congruent melting agent use of electrolyte.
Table 3
| Electrolyte | Cycle efficieny % first | Reversible capacity mAh/g | Irreversible capacity mAh/g |
| EC/DMC | 92.0 | 313.9 | 27.3 |
| TBP/DMC | 93.1 | 282.9 | 21.3 |
Embodiment 4: the preparation of lithium ion battery
Positive pole is prepared as follows: in mixer, carbon activity material (Osaka gas Company MCMB-10-28), 7wt% Kynoar (PVDF) and 3wt% acetylene black with 90wt% in use N-methyl-2 pyrrolidones (NMP) mix, obtain anode slurry, be coated in uniformly on the Copper Foil, then 130 ℃ of dryings.
Being prepared as follows of negative pole: in mixer, use in N-methyl-2 pyrrolidones (NMP) LiCoO with 90wt%
2(Sony), 6wt% Kynoar (PVDF) and 4wt% acetylene black mixes, and obtains cathode slurry, is coated on the aluminium foil 130 ℃ of dryings then uniformly.
By positive pole, negative pole and barrier film (celgard 2400) are wound up, inject example 2 and comparative example 1 electrolyte then respectively, make 18650 round lithium ion batteries.
Cell evaluation
Discharge and recharge experiment, at room temperature with battery charging and discharging to 4.2V, be discharged to 2.7V with the speed of 0.2C.Carry out the cryogenic property experiment again, condition is that battery is placed 4h at-20 ℃, and the speed with 0.2C is discharged to 2.7V then.Discharge and recharge experimental result and be shown in table 4.
Table 4
| Initial capacity (mAh) | Capacity (mAh) after 300 times circulates | Discharging efficiency at-20 ℃ | |
| Embodiment 2 | 1510 | 1263 | 81％～87％ |
| Comparative example 1 | 1530 | 1271 | 10％～24％ |
Claims (2)
1. a lithium-ion battery electrolytes that contains organic phosphorus compound is characterized in that it is by tributyl phosphate, LiPF
6Mix composition with dimethyl carbonate, wherein the volume ratio of dimethyl carbonate and tributyl phosphate is 1: 1, LiPF
6Content is 1mol/L.
2. by the described lithium-ion battery electrolytes that contains organic phosphorus compound of claim 1, it is anodal to it is characterized in that this battery adopts transition metal embedding lithium ionization compound to do, and charcoal material as cathode, porous polyolefin compound are barrier film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100161993A CN1306645C (en) | 2004-02-10 | 2004-02-10 | Lithium ion battery electrolyte containing organophosphorus compounds and battery formed thereby |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100161993A CN1306645C (en) | 2004-02-10 | 2004-02-10 | Lithium ion battery electrolyte containing organophosphorus compounds and battery formed thereby |
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| Publication Number | Publication Date |
|---|---|
| CN1558464A CN1558464A (en) | 2004-12-29 |
| CN1306645C true CN1306645C (en) | 2007-03-21 |
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| CNB2004100161993A Expired - Fee Related CN1306645C (en) | 2004-02-10 | 2004-02-10 | Lithium ion battery electrolyte containing organophosphorus compounds and battery formed thereby |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2330675B1 (en) * | 2008-09-11 | 2018-08-22 | NEC Corporation | Secondary battery |
| CN102473964B (en) * | 2009-08-04 | 2014-07-16 | 东曹氟技术株式会社 | Asymmetric and/or low-symmetry fluorine-containing phosphate ester for use in a nonaqueous electrolyte solution |
| CN102315483A (en) * | 2011-09-30 | 2012-01-11 | 湖南大学 | Novel multifunctional electrolyte |
| CN103151559A (en) * | 2013-02-05 | 2013-06-12 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte solution for lithium ion battery and corresponding lithium ion battery |
| CN103594729B (en) * | 2013-11-28 | 2015-11-18 | 深圳新宙邦科技股份有限公司 | A kind of electrolyte for lithium ion battery |
| CN105428715B (en) | 2015-11-04 | 2018-06-08 | 深圳新宙邦科技股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell and lithium ion battery |
| CN110247114A (en) | 2015-12-18 | 2019-09-17 | 深圳新宙邦科技股份有限公司 | A kind of electrolyte for lithium ion battery and lithium ion battery |
| CN105655631A (en) * | 2016-03-30 | 2016-06-08 | 武汉大学 | Incombustible sodium secondary battery, electrolyte thereof and application of incombustible sodium secondary battery |
| CN105655649A (en) * | 2016-03-30 | 2016-06-08 | 武汉大学 | Incombustible electro-deposition lithium battery and application thereof |
| CN106207257B (en) * | 2016-08-30 | 2018-12-11 | 浙江和也健康科技有限公司 | A kind of lithium battery electrolytes |
| CN108110311B (en) | 2016-11-25 | 2021-05-14 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
| CN108899582B (en) * | 2018-07-10 | 2021-05-04 | 中国科学院长春应用化学研究所 | Flame-retardant electrolyte and dual-ion battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001307768A (en) * | 2000-04-19 | 2001-11-02 | Toyota Central Res & Dev Lab Inc | Nonaqueous electrolyte secondary battery |
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2004
- 2004-02-10 CN CNB2004100161993A patent/CN1306645C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001307768A (en) * | 2000-04-19 | 2001-11-02 | Toyota Central Res & Dev Lab Inc | Nonaqueous electrolyte secondary battery |
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