CN102593510A - Electrolyte and lithium ion battery - Google Patents
Electrolyte and lithium ion battery Download PDFInfo
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- CN102593510A CN102593510A CN2011100019235A CN201110001923A CN102593510A CN 102593510 A CN102593510 A CN 102593510A CN 2011100019235 A CN2011100019235 A CN 2011100019235A CN 201110001923 A CN201110001923 A CN 201110001923A CN 102593510 A CN102593510 A CN 102593510A
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- lithium ion
- ion battery
- capacity
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 54
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 50
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000000654 additive Substances 0.000 claims abstract description 13
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000012964 benzotriazole Substances 0.000 claims abstract description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 11
- JOGCIHCXTAWPJI-UHFFFAOYSA-N carbonic acid;1,1,2,2-tetrafluoroethene Chemical compound OC(O)=O.FC(F)=C(F)F JOGCIHCXTAWPJI-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical class C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 7
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 150000002642 lithium compounds Chemical group 0.000 claims description 6
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 5
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract 2
- VUZHZBFVQSUQDP-UHFFFAOYSA-N 4,4,5,5-tetrafluoro-1,3-dioxolan-2-one Chemical compound FC1(F)OC(=O)OC1(F)F VUZHZBFVQSUQDP-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000004087 circulation Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012856 packing Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008094 contradictory effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- KWMBADTWRIGGGG-UHFFFAOYSA-N 2-diethoxyphosphorylacetonitrile Chemical compound CCOP(=O)(CC#N)OCC KWMBADTWRIGGGG-UHFFFAOYSA-N 0.000 description 1
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
Images
Classifications
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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
Abstract
The invention discloses an electrolyte and a lithium ion battery and belongs to the field of lithium ion batteries. The electrolyte solves the problem that the existing lithium ion battery has a low capacity and when charging voltage is higher than 4.2V, the existing lithium ion battery produces gas and expands so that cycling performances are poor and a service life is influenced. The electrolyte comprises lithium hexafluorophosphate, solvents and additives. The additives comprise a benzotriazole compound and perfluoroethylene carbonate The electrolyte can reduce a gas production amount in battery formation, prevent gas production and expansion of a battery, and improve a battery service life, a battery capacity and cycling performances. The lithium ion battery adopts the electrolyte so that charge cut-off voltage of the lithium ion battery is improved to 4.35V; a capacitance is improved by 15% and after 300 cycles, a capacitance is still 90% of the initial capacitance; the thickness of the lithium ion battery is changed by below 3%; and a service life is improved.
Description
Technical field
The present invention relates to the lithium ion battery field, particularly a kind of electrolyte and the lithium ion battery that contains this electrolyte.
Background technology
Lithium ion battery is high because of its working voltage, and energy density is high, characteristics such as have extended cycle life, and the development through nearly more than ten years has been widely used on all kinds of portable digital products, and flexible packing lithium ion battery is also used extremely extensive owing to its profile is changeable.But in recent years,, require battery to have higher capacity along with these machines high-effectization further.
For lithium ion battery obtains the higher capacity performance, the technical staff carries out the improvement and the modification of multiple performance usually to positive electrode, negative material.The lithium ion battery available capacity has direct relation with the lithium ion cell charging cut-ff voltage, and the charging cut-ff voltage is higher within the specific limits, and then the battery available capacity is higher; Certainly the charging cut-ff voltage of lithium ion battery can not infinitely improve, when the charging cut-ff voltage is higher than 4.2V, and reaction of battery generation gassing or the heating of battery generation internal short-circuit, electrolyte decomposition causes inner pressure of battery to increase, and bulging even blast can take place in battery.When the charging cut-ff voltage suitably was higher than 4.2V, though can effectively improve capacity of lithium ion battery, the gassing reaction of battery caused cycle performance of battery poor.The charging of lithium ion battery 4.2V at present is the optimal balance point that lithium ion battery guarantees battery capacity, the higher cycle performance of maintenance by voltage.
Summary of the invention
The objective of the invention is contradictory problems, provide a kind of and can either improve battery capacity, can keep the lithium-ion battery electrolytes of higher cycle performance again to above-mentioned capacity of lithium ion battery and cycle performance of battery.
Another object of the present invention provides the lithium ion battery of a kind of high power capacity, high cycle performance.
To achieve these goals, the present invention has adopted following technical scheme:
The invention discloses a kind of lithium-ion battery electrolytes, said electrolyte comprises lithium hexafluoro phosphate, solvent and additive, and said additive comprises benzotriazole compound and perfluoro ethylene carbonate.
Among the present invention, said additive also comprises one or both in methyl phenyl ethers anisole, the diethyl phosphonate.
The consumption of said BTA compounds and perfluoro ethylene carbonate is respectively the 0.1%-5% of electrolyte gross mass, is preferably 1%-5%, more preferably 3.5%-5%.
The consumption of one or both in said methyl phenyl ethers anisole, the diethyl phosphonate is respectively the 1.5-2.5% of electrolyte gross mass, is preferably 2%.
Among the present invention, said solvent comprises ethylene carbonate, methyl ethyl carbonate, diethyl carbonate, and ethylene carbonate: methyl ethyl carbonate: the volume ratio of diethyl carbonate is 1.8-2.2: 0.8-1.2: 3.8-4.2; Said hexafluorophosphoric acid lithium concentration is 1.1-1.3mol/L.
Ethylene carbonate in the embodiments of the invention: methyl ethyl carbonate: the volume ratio of diethyl carbonate is 2: 1: 4; Said hexafluorophosphoric acid lithium concentration is 1.2mol/L.It is pointed out that the adjustment in the scope that test allows of aforementioned proportion (2: 1: 4) or concentration (1.2mol/L) changes, and can not influence the beneficial effect in the embodiments of the invention.
The invention also discloses a kind of lithium ion battery, said battery comprises electrolyte, and by containing the anode pole piece that the active lithium compound forms, and containing the cathode pole piece that graphitized carbon is prepared from, said electrolyte is the disclosed electrolyte of the invention described above; The meso-position radius of said active lithium compound is 18-19 μ m, and specific area is 0.15-0.25m
2/ g, the compacted density of said anode pole piece is 3.7-3.8g/cm
3, the performance of 1C capacity is 150-170mA/g; The meso-position radius of said graphitized carbon is 20-21 μ m, and specific area is 1.6-1.7m
2/ g, the compacted density of said cathode pole piece is 1.5-1.6g/cm
3, the performance of 1C capacity is 330-360mA/g.
In the embodiments of the invention, the main component of said active lithium compound is a cobalt acid lithium; The main component of said graphitized carbon is a native graphite.
Because adopt above technical scheme, beneficial effect of the present invention is:
Adopt the lithium ion battery of electrolyte preparation disclosed by the invention; Solved the contradictory problems of battery capacity and cycle performance of battery; The battery charge cut-ff voltage is brought up to 4.35V; It is about 15% to effectively raise the capacity of lithium ion battery, and its charge-discharge performance is good, and circulating, capacity still can keep 90% of initial capacity after 300 times.In addition; The passivating film that electrolyte of the present invention and lithium ion battery can form a kind of densification on the positive pole and the negative material surface of battery; Reduced the gas production of battery when changing into; When having overcome present conventional lithium ion cell charging voltage and being higher than 4.2V because the gassing reaction, the problem in expansion effects battery outward appearance and useful life; After 300 circulations, cell thickness changes less than 3%, and the battery outward appearance does not almost change, the useful life of having improved battery.
Description of drawings
Fig. 1 is battery capacity-voltage curve of (4.35V) under high voltage in the embodiment of the invention;
The cycle-index that Fig. 2 discharges and recharges under high voltage (4.35V) for battery in the embodiment of the invention and the curve chart of capability retention;
Fig. 3 is after battery circulates through 300 times in the embodiment of the invention, the front appearance figure of flexible packing lithium ion battery;
Fig. 4 is after battery circulates through 300 times in the embodiment of the invention, the side outside drawing of flexible packing lithium ion battery;
Fig. 5 is the capacity-voltage curve of (4.2V) under conventional voltage of battery in the Comparative Examples 1 of the present invention;
Fig. 6 is the capacity-voltage curve of (4.35V) under high voltage of battery in the Comparative Examples 2 of the present invention;
The cycle-index that Fig. 7 discharges and recharges under high voltage (4.35V) for battery in the Comparative Examples 2 of the present invention and the curve chart of capability retention;
Fig. 8 is after battery circulates through 200 times in the Comparative Examples 2 of the present invention, the front appearance figure of flexible packing lithium ion battery;
Fig. 9 is after battery circulates through 200 times in the Comparative Examples 2 of the present invention, the side outside drawing of flexible packing lithium ion battery.
Embodiment
The capacity of lithium ion battery can increase with the charging voltage of battery, and the charging cut-ff voltage that therefore improves battery can effectively improve battery capacity.But the charging cut-ff voltage of lithium ion battery can not infinitely improve, when the charging cut-ff voltage is higher than 4.2V, and reaction of battery generation gassing or the heating of battery generation internal short-circuit, electrolyte decomposition causes inner pressure of battery to increase, and bulging even blast can take place in battery.The flexible packing lithium ion battery of plastic-aluminum shell particularly, when charging voltage was higher than 4.2V, its shell generation bulging caused the battery bad order, and simultaneously because the soft texture of flexible-packed battery, compaction force is not enough, very easily produces shedding, shortens the life-span of battery.
Add additive BTA compounds and perfluoro ethylene carbonate in the electrolyte of the present invention, also added in methyl phenyl ethers anisole, diethyl (cyano methyl) phosphonate ester one or both simultaneously; Wherein the consumption of BTA compounds and perfluoro ethylene carbonate is respectively the 0.1%-5% of electrolyte gross mass, is preferably 1%-5%, more preferably 3.5%-5%; The consumption of one or both in methyl phenyl ethers anisole, diethyl (cyano methyl) phosphonate ester is respectively the 1.5-2.5% of electrolyte gross mass, is preferably 2%.It is ethylene carbonate, methyl ethyl carbonate and the diethyl carbonate of 1.8-2.2: 0.8-1.2: 3.8-4.2 that said electrolyte has also added volume ratio, and concentration is the lithium hexafluoro phosphate of 1.1-1.3mol/L; In the embodiments of the invention, the ratio of ethylene carbonate, methyl ethyl carbonate and diethyl carbonate is 2: 1: 4, and the hexafluorophosphoric acid lithium concentration is 1.2mol/L.Use through the collocation of the positive and negative pole material among electrolyte and the present invention, make lithium ion battery provided by the invention when being charged to high voltage (4.35V), promptly effectively raise battery capacity, having does not influence its charge-discharge performance.Because the adding of additive has stoped the gassing reaction of electrolyte, reaches the effect of the bad order of preventing that inflatable causes, and prolongs the useful life of battery.Concrete, in order to reach the raising battery capacity, improve cycle performance of battery, improve the battery purpose in useful life, the meso-position radius of used cell positive material is 18.75 μ m in the embodiment of the invention; Specific area is 0.2m
2/ g; The compacted density of anode pole piece is 3.7-3.8g/cm
31C capacity performance 150-170mA/g.Simultaneously, the meso-position radius of cell negative electrode material is 20.65 μ m; Specific area is 1.64m
2/ g; The compacted density of said cathode pole piece is 1.5-1.6g/cm
31C capacity performance 330-360mA/g.
Through specific embodiment and Comparative Examples the present invention is done further explain below.Following examples and Comparative Examples are only further explained the present invention, should not be construed as limitation of the present invention.
Embodiment
1. battery system characteristic
Battery size: 624199P; Anodal system: cobalt acid lithium (coat, mix); Negative pole system: native graphite.Cobalt acid lithium physicochemical property: D50 is 18.75 μ m; Specific area is 0.2m
2/ g; The pole piece compacted density is 3.7～3.8g/cm
3 1C capacity performance 150～170mA/g; Native graphite: D50 is 20.65 μ m; Specific area is 1.64m
2/ g; The pole piece compacted density is 1.5～1.6g/cm
31C capacity performance 330～360mA/g.
Electrolyte system: EC/EMC/DEC (volume ratio: 2: 1: 4), lithium concentration (Li+): 1.2mol/L; Additive is BTA compounds 2% (percentage of electrolyte total weight), perfluoro ethylene carbonate 2% (percentage of electrolyte total weight).
2. battery capacity measuring
Adopt blue electro-detection cabinet test battery capacity, concrete operations are following: (1) constant current (0.5C) is discharged to 3.0V; (2) constant current (0.5C) charges to 4.35V; (3) constant voltage (4.35V) charges to electric current and ends less than 10mA; (4) leave standstill 5min; (5) constant current (0.5C) is discharged to 3.0V.
According to above-mentioned condition, the battery capacity measuring result is greater than 3390mAh (table 1), capacity-voltage curve (Fig. 1).
Table 1 capacitance is measured the result
| Battery (group) | Discharge capacity of the cell/mAh |
| 1 | 3393 |
| 2 | 3394 |
| 3 | 3391 |
3. cycle performance test
Adopt blue electro-detection cabinet test battery cycle performance, concrete operations are following:
(1) constant current (0.5C) is discharged to 3.0V;
(2) constant current (0.5C) charges to 4.35V;
(3) constant voltage (4.35V) charges to electric current and ends less than 10mA;
(4) leave standstill 5min;
(5) constant current (0.5C) is discharged to 3.0V
(6) and then from work step 2 begin new circulation, stop until 300 times.
After the charge and discharge cycles 300 times, battery capacity keeps 90% (Fig. 2) of initial capacity in above-mentioned voltage range, and the battery battery core varied in thickness is less than 3% (table 2), and the battery outward appearance keeps the state before the circulation, almost not distortion (Fig. 3, Fig. 4).
The test of table 2 battery battery core varied in thickness
| Thickness (mm) before the circulation | Circulation back thickness (mm) | Thickness change (%) |
| 6.19 | 6.35 | 2.58％ |
| 6.17 | 6.24 | 1.13％ |
| 6.17 | 6.28 | 1.78％ |
In addition, the present invention has replenished embodiment 2-9 according to the additive level (said additive level percentage composition is the percentage of electrolyte total weight) of table 3 under the constant situation of battery characteristics condition and loop test mode.And measured when in above-mentioned voltage range, discharging and recharging, battery capacity still can keep the cycle-index of 90% initial capacity, measures the result and sees table 3.In the table, " efficient >=90% ", promptly battery capacity keeps at least 90% of initial capacity.
The result is measured in the circulation of table 3 battery
Comparative Examples 1
1. conventional flexible-packed battery architectural feature
Battery size: 624199P; Anodal system: cobalt acid lithium (coat, mix); Negative pole system: native graphite.Cobalt acid lithium physicochemical property: D50 is 18.75 μ m; Specific area is 0.2m
2/ g; The pole piece compacted density is 3.7～3.8g/cm
3 1C capacity performance 150～170ma/g; Native graphite: D50 is 20.65 μ m; Specific area is 1.64m
2/ g; The pole piece compacted density is 1.5～1.6g/cm
31C capacity performance 330～360mA/g.
Electrolyte system: EC/EMC/DEC (volume ratio: 2: 1: 4), lithium concentration (Li+): 1.2mol/L.
2. the mensuration of battery capacity under conventional voltage
Adopt blue electro-detection cabinet test battery capacity, concrete steps are following:
(1) constant current (0.5C) is discharged to 3.0V;
(2) constant current (0.5C) charges to 4.2V;
(3) constant voltage (4.2V) charges to electric current and ends less than 10mA;
(4) leave standstill 5min;
(5) constant current (0.5C) is discharged to 3.0V;
According to above-mentioned condition, the conventional flexible-packed battery capacity that (4.2V) measures under conventional voltage is less, all less than 3000mAh (table 4), and capacity-voltage curve (Fig. 5).Compare with the battery of the electrolyte preparation of adopting among the embodiment of the present invention, electrolyte and lithium ion battery that the present invention announces have improved battery capacity about 15%.
The battery capacity of the conventional flexible packing lithium ion battery of table 4 under conventional voltage
| Battery (group) | Battery capacity/mAh |
| 1 | 2932 |
| 2 | 2934 |
| 3 | 2937 |
Comparative Examples 2
1. conventional flexible-packed battery architectural feature
Battery size: 624199P; Anodal system: cobalt acid lithium (coat, mix); Negative pole system: native graphite.Cobalt acid lithium physicochemical property: D50 is 18.75 μ m; Specific area is 0.2m
2/ g; The pole piece compacted density is 3.7～3.8g/cm
3 1C capacity performance 150～170mA/g; Native graphite: D50 is 20.65 μ m; Specific area is 1.64m
2/ g; The pole piece compacted density is 1.5～1.6g/cm
31C capacity performance 330～360mA/g.
Electrolyte system: EC/EMC/DEC (volume ratio: 2: 1: 4), lithium concentration (Li+): 1.2mol/L.
2. the mensuration of battery capacity under high voltage
Adopt blue electro-detection cabinet test battery capacity, concrete steps are following:
(1) constant current (0.5C) is discharged to 3.0V;
(2) constant current (0.5C) charges to 4.35V;
(3) constant voltage (4.35V) charges to electric current and ends less than 10mA;
(4) leave standstill 5min;
(5) constant current (0.5C) is discharged to 3.0V;
Under the situation that improves charging voltage, the capacitance of conventional batteries also increases by (table 5), voltage-capacity curve (Fig. 6)., voltage still can arrive higher battery capacity though it is pointed out that conventional flexible-packed battery when being brought up to 4.35V, because the gassing reaction causes battery to expand, not only have a strong impact on outward appearance, also influence the useful life of battery.Compare with embodiments of the invention, adopt the lithium ion battery of electrolyte preparation provided by the invention, when improving battery capacity, have no the bad reaction that influences battery outward appearance and life-span.
The battery capacity of the conventional flexible packing lithium ion battery of table 5 under high voltage
| Battery (group) | Battery capacity/mAh |
| 1 | 3432 |
| 2 | 3439 |
| 3 | 3438 |
3. cycle performance test
Adopt blue electro-detection cabinet test battery cycle performance, concrete operations are following:
(1) constant current (0.5C) is discharged to 3.0V;
(2) constant current (0.5C) charges to 4.35V;
(3) constant voltage (4.35V) charges to electric current and ends less than 10mA;
(4) leave standstill 5min;
(5) constant current (0.5C) is discharged to 3.0V
(6) and then from work step 2 begin new circulation, stop until 300 times.
Under above-mentioned measuring condition, though conventional flexible packing lithium ion battery adopts high charge voltage can improve battery capacity accordingly, its cycle performance is poor; Only through 200 circulations; Its battery capacity just drops to about 80% (Fig. 7) of initial capacity, and cell thickness variation obvious (table 6), and it is serious to expand; Battery outward appearance serious distortion (Fig. 8, Fig. 9) influences battery and uses.Compare with embodiments of the invention; The lithium ion battery of electrolyte provided by the invention and preparation thereof; The battery charge cut-ff voltage is brought up to 4.35V, effectively raise about 15% (table 1) of capacity of lithium ion battery, and the capacity after 300 times of circulating still can keep 90% (Fig. 1) of initial capacity; In addition, battery through 300 times the circulation after, outward appearance almost constant (Fig. 3, Fig. 4), cell thickness changes less than 3% (table 2), has improved the useful life of battery.
The test of table 6 battery battery core varied in thickness
| Thickness (mm) before the circulation | Circulation back thickness (mm) | Thickness change (%) |
| 6.23 | 9.00 | 44.46％ |
| 6.21 | 10.94 | 76.17％ |
| 6.17 | 10.20 | 65.32％ |
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, can also make some simple deduction or replace, all should be regarded as belonging to protection scope of the present invention.
Claims (10)
1. lithium-ion battery electrolytes, said electrolyte comprises lithium hexafluoro phosphate, solvent and additive, it is characterized in that: said additive comprises benzotriazole compound and perfluoro ethylene carbonate.
2. electrolyte according to claim 1 is characterized in that: said additive also comprises one or both in methyl phenyl ethers anisole, the diethyl phosphonate.
3. electrolyte according to claim 1 is characterized in that: the consumption of said BTA compounds and perfluoro ethylene carbonate is respectively the 0.1%-5% of electrolyte gross mass.
4. electrolyte according to claim 1 is characterized in that: the consumption of said BTA compounds and perfluoro ethylene carbonate is respectively the 1%-5% of electrolyte gross mass.
5. electrolyte according to claim 1 is characterized in that: the consumption of said BTA compounds and perfluoro ethylene carbonate is respectively the 3.5%-5% of electrolyte gross mass.
6. electrolyte according to claim 2 is characterized in that: the consumption of one or both in said methyl phenyl ethers anisole, the diethyl phosphonate is respectively the 1.5-2.5% of electrolyte gross mass.
7. electrolyte according to claim 2 is characterized in that: the consumption of one or both in said methyl phenyl ethers anisole, the diethyl phosphonate is respectively 2% of electrolyte gross mass.
8. according to each described electrolyte of claim 1-7; It is characterized in that: said solvent comprises ethylene carbonate, methyl ethyl carbonate, diethyl carbonate, and ethylene carbonate: methyl ethyl carbonate: the volume ratio of diethyl carbonate is 1.8-2.2: 0.8-1.2: 3.8-4.2; Said hexafluorophosphoric acid lithium concentration is 1.1-1.3mol/L.
9. lithium ion battery; Said battery comprises electrolyte; By containing the anode pole piece that the active lithium compound forms, and containing the cathode pole piece that graphitized carbon is prepared from, it is characterized in that: said electrolyte is each described electrolyte of claim 1-8; The meso-position radius of said active lithium compound is 18-19 μ m, and specific area is 0.15-0.25m
2/ g, the compacted density of said anode pole piece is 3.7-3.8g/cm
3, the performance of 1C capacity is 150-170mA/g; The meso-position radius of said graphitized carbon is 20-21 μ m, and specific area is 1.6-1.7m
2/ g, the compacted density of said cathode pole piece is 1.5-1.6g/cm
3, the performance of 1C capacity is 330-360mA/g.
10. lithium ion battery according to claim 9 is characterized in that: the main component of said active lithium compound is a cobalt acid lithium; The main component of said graphitized carbon is a native graphite.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110001923.5A CN102593510B (en) | 2011-01-06 | 2011-01-06 | A kind of electrolyte and lithium ion battery |
| HK13100296.6A HK1173852A1 (en) | 2011-01-06 | 2013-01-09 | Electrolyte and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110001923.5A CN102593510B (en) | 2011-01-06 | 2011-01-06 | A kind of electrolyte and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102593510A true CN102593510A (en) | 2012-07-18 |
| CN102593510B CN102593510B (en) | 2016-03-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110001923.5A Active CN102593510B (en) | 2011-01-06 | 2011-01-06 | A kind of electrolyte and lithium ion battery |
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| Country | Link |
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| CN (1) | CN102593510B (en) |
| HK (1) | HK1173852A1 (en) |
Cited By (11)
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| KR20160002315A (en) * | 2014-06-30 | 2016-01-07 | 솔브레인 주식회사 | Electrolyte and lithium secondary battery with the same |
| CN110333455A (en) * | 2019-06-05 | 2019-10-15 | 合肥国轩高科动力能源有限公司 | A kind of electrically separated positive and negative anodes of Symmetrical cells charge and discharge produce the method and its application of gas |
| CN111082129A (en) * | 2019-12-24 | 2020-04-28 | 东莞新能源科技有限公司 | Electrochemical device and electronic device |
| CN111987359A (en) * | 2019-11-27 | 2020-11-24 | 中节能万润股份有限公司 | Novel lithium ion battery electrolyte additive and application thereof |
| CN112290095A (en) * | 2020-10-26 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Lithium ion battery electrolyte suitable for high-nickel material system and preparation method thereof |
| CN113067035A (en) * | 2021-03-30 | 2021-07-02 | 湖南师范大学 | Formula of lithium-sulfur battery electrolyte |
| CN113871715A (en) * | 2020-06-30 | 2021-12-31 | 诺莱特电池材料(苏州)有限公司 | Lithium iron phosphate battery |
| CN114114055A (en) * | 2022-01-25 | 2022-03-01 | 天津力神电池股份有限公司 | Method for rapidly evaluating cycle performance of lithium ion soft package battery system |
| US20220131189A1 (en) * | 2020-10-28 | 2022-04-28 | Hyundai Motor Company | Electrolyte solution for lithium secondary battery and lithium secondary battery comprising same |
| WO2023177162A1 (en) * | 2022-03-16 | 2023-09-21 | 주식회사 엘지에너지솔루션 | Lithium secondary battery |
| US11837698B2 (en) | 2019-12-24 | 2023-12-05 | Dongguan Amperex Technology Limited | Electrochemical device and electronic device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102371079B1 (en) * | 2014-06-30 | 2022-03-10 | 솔브레인 주식회사 | Electrolyte and lithium secondary battery with the same |
| KR20160002315A (en) * | 2014-06-30 | 2016-01-07 | 솔브레인 주식회사 | Electrolyte and lithium secondary battery with the same |
| CN110333455A (en) * | 2019-06-05 | 2019-10-15 | 合肥国轩高科动力能源有限公司 | A kind of electrically separated positive and negative anodes of Symmetrical cells charge and discharge produce the method and its application of gas |
| CN110333455B (en) * | 2019-06-05 | 2021-10-01 | 合肥国轩高科动力能源有限公司 | Method for separating gas production from positive electrode and negative electrode through charge and discharge of symmetrical battery and application of method |
| CN111987359B (en) * | 2019-11-27 | 2021-07-16 | 中节能万润股份有限公司 | Novel lithium ion battery electrolyte additive and application thereof |
| CN111987359A (en) * | 2019-11-27 | 2020-11-24 | 中节能万润股份有限公司 | Novel lithium ion battery electrolyte additive and application thereof |
| CN111082129B (en) * | 2019-12-24 | 2021-01-12 | 东莞新能源科技有限公司 | Electrochemical device and electronic device |
| CN111082129A (en) * | 2019-12-24 | 2020-04-28 | 东莞新能源科技有限公司 | Electrochemical device and electronic device |
| US11837698B2 (en) | 2019-12-24 | 2023-12-05 | Dongguan Amperex Technology Limited | Electrochemical device and electronic device |
| CN113871715A (en) * | 2020-06-30 | 2021-12-31 | 诺莱特电池材料(苏州)有限公司 | Lithium iron phosphate battery |
| CN112290095A (en) * | 2020-10-26 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Lithium ion battery electrolyte suitable for high-nickel material system and preparation method thereof |
| US20220131189A1 (en) * | 2020-10-28 | 2022-04-28 | Hyundai Motor Company | Electrolyte solution for lithium secondary battery and lithium secondary battery comprising same |
| US11670801B2 (en) * | 2020-10-28 | 2023-06-06 | Hyundai Motor Company | Electrolyte solution for lithium secondary battery and lithium secondary battery comprising same |
| CN113067035A (en) * | 2021-03-30 | 2021-07-02 | 湖南师范大学 | Formula of lithium-sulfur battery electrolyte |
| CN114114055A (en) * | 2022-01-25 | 2022-03-01 | 天津力神电池股份有限公司 | Method for rapidly evaluating cycle performance of lithium ion soft package battery system |
| WO2023177162A1 (en) * | 2022-03-16 | 2023-09-21 | 주식회사 엘지에너지솔루션 | Lithium secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1173852A1 (en) | 2013-05-24 |
| CN102593510B (en) | 2016-03-09 |
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