CN102420340A - Manufacturing method of battery - Google Patents
Manufacturing method of battery Download PDFInfo
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- CN102420340A CN102420340A CN201110329768XA CN201110329768A CN102420340A CN 102420340 A CN102420340 A CN 102420340A CN 201110329768X A CN201110329768X A CN 201110329768XA CN 201110329768 A CN201110329768 A CN 201110329768A CN 102420340 A CN102420340 A CN 102420340A
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a manufacturing method of a battery, which comprises the following steps of: injecting electrolyte to a battery shell through a liquid injecting port on the battery shell for carrying out open formation, and when a stable solid electrolyte interfacial film is formed on the surface of a negative electrode of the battery through the open formation, adding a flame-retardant additive to seal off the liquid injection port. According to the technical scheme of the manufacturing method, as the electrolyte is firstly added, the electrolyte forms the stable SEI (Solid Electrolyte Interfacial) film on the surface of the negative electrode of the battery, and then the flame-retardant additive is added to be prevented from participating in the formation of the SEI film on the surface of the negative electrode, so that the formed SEI (Solid Electrolyte Interfacial) film is stable and the cycling performance of the battery is increased.
Description
Technical field
The present invention relates to battery and make the field, be specifically related to the manufacture method of battery.
Background technology
Under the effect of factors such as guiding of the breakthrough of the powerful demand of current portable electronic device market, new material new technology and application and national new forms of energy policy, lithium ion battery has obtained development at full speed owing to having advantages such as high-energy-density, high voltage, volume be little, in light weight.
Yet; The electrolyte of lithium ion battery is made up of inflammable organic solvent and lithium salts at present; And because battery can be emitted great amount of heat in use; Make these organic solvents and steam thereof catch fire easily initiation fire even blast, directly cause the safety problem of lithium ion battery, influenced the extensive use of lithium ion battery.In addition, the frequent abuse of battery, as overcharge, short circuit, be heated, clashed etc. exothermic reaction possibly take place also maybe on fire even blast when battery temperature is higher than certain value, and this on firely mainly cause by electrolyte.
At present; Improving the most frequently used method of lithium ion battery security is in electrolyte, to add flame-retardant additive; The adding of flame-retardant additive can make inflammable organic electrolyte become difficult combustion or non-flammable electrolyte; Reduce battery heat release value and self-heating rate, also increase the stability of electrolyte self simultaneously, avoid burning or the blast of battery under overheated condition.At present research is more has phosphate, phosphite ester, halogenated carboxylic ester, phosphonitrile compounds and halogen ether etc., but these flame-retardant additives are in general all more or less to the performance of battery, and especially cycle performance is influential.This mainly is because these flame-retardant additives can be participated in the formation of negative terminal surface SEI film; Make that the SEI film that forms is unstable; Then cause the decline such as capacity, high rate performance of battery, and, in the follow-up cyclic process of battery; Electrolyte component can continue to be reduced, thereby causes the decline of cycle performance of battery etc.
Summary of the invention
The embodiment of the invention provides a kind of manufacture method of battery, and the manufacture method of said battery can stop flame-retardant additive to participate in the formation of negative terminal surface SEI film, makes that the SEI film that forms is stable, has improved the cycle performance of battery.
A kind of manufacture method of battery comprises:
Electrolyte is injected into through the liquid injection port on the battery case carries out opening in the battery case and change into;
When the negative terminal surface of battery through described opening change into form stable solid electrolyte interface film after, add flame-retardant additive;
Seal said liquid injection port.
Preferably, after said negative terminal surface when battery forms stable solid electrolyte interface film, add after the flame-retardant additive, before sealing said liquid injection port, said method also comprises: carry out the ageing operation, to detect the performance of battery.
Preferably, said flame-retardant additive is a trimethyl phosphate, triethyl phosphate, triethyl phosphite, trifluoroethyl phosphate, six-trifluoroethyl tripolyphosphazene, a kind of or both perhaps many persons' the combinations arbitrarily in the perfluoro diethyl ether.
Preferably, said flame-retardant additive is 1%～50% with respect to the weight percentage of electrolyte quality.
Preferably, said flame-retardant additive is 10%～40% with respect to the weight percentage of electrolyte quality.
Preferably, said flame-retardant additive is a trimethyl phosphate, and said trimethyl phosphate is 10%～30% with respect to the weight percentage of electrolyte quality.
Preferably, said flame-retardant additive is a triethyl phosphate, and said triethyl phosphate is 20% with respect to the weight percentage of electrolyte quality.
Preferably, said flame-retardant additive is a triethyl phosphite, and said triethyl phosphite is 20% with respect to the weight percentage of electrolyte quality.
Preferably, said flame-retardant additive is the trifluoroethyl phosphate, and said trifluoroethyl phosphate is 20% with respect to the weight percentage of electrolyte quality.
Preferably, when said flame-retardant additive was six-trifluoroethyl tripolyphosphazene, said six-trifluoroethyl tripolyphosphazene was 10% with respect to the weight percentage of electrolyte quality.
Preferably, said flame-retardant additive is the perfluoro diethyl ether, and said perfluoro diethyl ether is 30% with respect to the weight percentage of electrolyte quality.
The manufacture method of the battery that the embodiment of the invention provides; Electrolyte is injected into through the liquid injection port on the battery case carries out opening in the battery case and change into; When the negative terminal surface of battery through described opening change into form stable solid electrolyte interface film after; Add flame-retardant additive, seal said liquid injection port.When preparing the electrolyte of battery, needed flame-retardant additive is added electrolyte together, then with of the prior art; All electrolyte components comprise flame-retardant additive, inject battery case together; Carry out other step that battery is made subsequently, the method that comprise ageing, seal, changes into is compared, the manufacture method of the battery that the embodiment of the invention provides; Can stop flame-retardant additive to participate in the formation of negative terminal surface SEI film, make that the SEI film that forms is stable, improve the cycle performance of battery.
Figure of description
Fig. 1 is a battery production method schematic flow sheet in the embodiment of the invention.
Embodiment
The embodiment of the invention provides a kind of manufacture method of battery, and the manufacture method of said battery can stop flame-retardant additive to participate in the formation of negative terminal surface SEI film, makes that the SEI film that forms is stable, has improved the cycle performance of battery.Below be elaborated.
Consult Fig. 1, the manufacture method of a kind of battery provided by the invention comprises:
101, electrolyte is injected into through the liquid injection port on the battery case carries out opening in the battery case and change into.
Change in battery making field and be meant that negative pole forms the process of solid electrolyte interface film (SEI, solide electrolyte interface), opening is meant that liquid injection port is not sealed.
Electrode material and electrolyte in the lithium ion battery react on solid-liquid phase interface; Form the passivation layer that one deck is covered in electrode material surface; This passivation layer is a kind of boundary layer, has the characteristic of solid electrolyte, and this passivation layer is the excellence conductor of electronic body lithium ion; Lithium ion can pass through this passivation layer and freely embed and deviate from; Therefore this layer passivation layer is called as the solid electrolyte interface film, and anodal surface also has the SEI film to form, and just the SEI film on anodal surface will be far smaller than the SEI film of negative terminal surface to the influence of battery.
The electrolyte of mentioning among the present invention does not comprise flame-retardant additive, when manufacture batteries, earlier electrolyte is injected in the battery case through liquid injection port, and said electrolyte and GND surface form the SEI film.
102, when the negative terminal surface of battery through described opening change into form stable solid electrolyte interface film after, add flame-retardant additive.
After said electrolyte and GND surface form stable SEI film, add flame-retardant additive, flame-retardant additive just can not participated in the formation of SEI film like this.
Said flame-retardant additive is a trimethyl phosphate, triethyl phosphate, triethyl phosphite, trifluoroethyl phosphate, six-trifluoroethyl tripolyphosphazene, a kind of or both perhaps many persons' the combinations arbitrarily in the perfluoro diethyl ether.
Said flame-retardant additive is a trimethyl phosphate; Triethyl phosphate, triethyl phosphite, trifluoroethyl phosphate; Six-trifluoroethyl tripolyphosphazene; In the perfluoro diethyl ether one of or when combination, said flame-retardant additive is 1%～50% with respect to the weight percentage of electrolyte quality, preferred said flame-retardant additive is 10%～40% with respect to the weight percentage of electrolyte quality.
When said flame-retardant additive was trimethyl phosphate, said trimethyl phosphate was 10%～30% with respect to the weight percentage of electrolyte quality.
When said flame-retardant additive was triethyl phosphate, said triethyl phosphate was 20% with respect to the weight percentage of electrolyte quality.
When said flame-retardant additive was triethyl phosphite, said triethyl phosphite was 20% with respect to the weight percentage of electrolyte quality.
When said flame-retardant additive was the trifluoroethyl phosphate, said trifluoroethyl phosphate was 20% with respect to the weight percentage of electrolyte quality.
When said flame-retardant additive was six-trifluoroethyl tripolyphosphazene, said six-trifluoroethyl tripolyphosphazene was 10% with respect to the weight percentage of electrolyte quality.
When said flame-retardant additive was the perfluoro diethyl ether, said perfluoro diethyl ether was 30% with respect to the weight percentage of electrolyte quality.
Above-mentioned is when being one-component with the flame-retardant additive; Every kind of component is introduced with respect to the concrete percentage composition of electrolyte; In fact; Flame-retardant additive can be the combination of trimethyl phosphate and triethyl phosphate, and the percentage composition of two kinds of components is 10%～40% with respect to the percentage composition of electrolyte quality.Can certainly be the combination of other components, be 1%～50% as long as the quality after all components addition is the weight percentage of electrolyte quality.
103, carry out the ageing operation, to detect the performance of battery.
Ageing is meant in battery is made battery in varying environment held a period of time, with the performance of test battery, as whether can smolder, on fire or blast etc.
104, seal said liquid injection port.
Seal and be meant the liquid injection port complete closed.
The manufacture method of the battery that the embodiment of the invention provides is injected into electrolyte and carries out opening in the battery case and change into through the liquid injection port on the battery case; When the negative terminal surface of battery through described opening change into form stable solid electrolyte interface film after, add flame-retardant additive; After the ageing, seal said liquid injection port.When preparing the electrolyte of battery, needed flame-retardant additive is added electrolyte together, then with of the prior art; All electrolyte components comprise flame-retardant additive, inject battery case together; Carry out other step that battery is made subsequently, the method that comprise ageing, seal, changes into is compared, the manufacture method of the battery that the embodiment of the invention provides; Can stop flame-retardant additive to participate in the formation of negative terminal surface SEI film, make that the SEI film that forms is stable, improve the cycle performance of battery.
Alternatively, in the above-described embodiments, step 103 can be omitted.
For lithium rechargeable battery, no matter be square, cylindrical or soft-package battery, no matter be takeup type or stacked also, adopt the described method of the embodiment of the invention can both obtain identical effect.Making and test with square coiled lithium-ion secondary battery (model is 453450A) is example below, and the embodiment of the invention is further explained.
The method that first lithium battery adopts the embodiment of the invention to provide is made, and wherein flame-retardant additive is a trimethyl phosphate, and said trimethyl phosphate is 10% with respect to the weight percentage of electrolyte quality.
The method that second lithium battery adopts the embodiment of the invention to provide is made, and wherein flame-retardant additive is a trimethyl phosphate, and said trimethyl phosphate is 30% with respect to the weight percentage of electrolyte quality.
The method that the 3rd lithium battery adopts the embodiment of the invention to provide is made, and wherein flame-retardant additive is a triethyl phosphate, and said triethyl phosphate is 20% with respect to the weight percentage of electrolyte quality.
The method that the 4th lithium battery adopts the embodiment of the invention to provide is made, and wherein flame-retardant additive is a triethyl phosphite, and said triethyl phosphite is 20% with respect to the weight percentage of electrolyte quality.
The method that the 5th lithium battery adopts the embodiment of the invention to provide is made, and wherein flame-retardant additive is the trifluoroethyl phosphate, and said trifluoroethyl phosphate is 20% with respect to the weight percentage of electrolyte quality.
The method that the 6th lithium battery adopts the embodiment of the invention to provide is made, and wherein flame-retardant additive is six-trifluoroethyl tripolyphosphazene, and said six-trifluoroethyl tripolyphosphazene is 10% with respect to the weight percentage of electrolyte quality.
The method that the 7th lithium battery adopts the embodiment of the invention to provide is made, and wherein flame-retardant additive is the perfluoro diethyl ether, and said perfluoro diethyl ether is 30% with respect to the weight percentage of electrolyte quality
The battery that the 8th lithium battery adopts conventional method to make does not add any flame-retardant additive.
The manufacture method of the 9th lithium battery is when preparing electrolyte, and the trimethyl phosphate that in electrolyte, adds 10% weight content is as flame-retardant additive, and this flame-retardant additive changes into, seals with disposable being injected in the battery of electrolyte.
The manufacture method of the tenth lithium battery is when preparing electrolyte, and the trifluoroethyl phosphate that in electrolyte, adds 20% weight content is as flame-retardant additive, and this flame-retardant additive changes into, seals with disposable being injected in the battery of electrolyte.
Ten kinds of batteries making in the face of three kinds of manufacture methods of above-mentioned employing down carry out the security performance of battery, the capacity of battery, the multiplying power discharging capacity of battery, the cycle performance test of battery:
The security performance test of battery:
With lithium battery test cabinet will be above-mentioned nine kinds completely electric attitude batteries be limited to 4.2V in the charging with 1C constant-current constant-voltage charging 2.5 hours, be charged to 5V crossing battery with 1C then, phenomenons such as whether recording cell occurs is smoldered, burning, on fire, blast; Place the outside to have on the wire netting of protective device on battery, directly battery is heated with liquefied gas flame below, phenomenons such as whether recording cell smolders, burning, on fire, blast.Test result is seen table 1.
Table 1: battery safety test chart
Test result by table 1 can be found out; The battery (first lithium battery to the, seven lithium batteries) that adopts method of the present invention preparation with adopt directly that flame-retardant additive is added in the battery (the 9th lithium battery) that the method for a fluid injection in the electrolyte prepares is the same; Overcharge in the test at 1C-5V; To smolder all do not appear in battery, the phenomenon of on fire or blast, and the phenomenon of smoldering has then appearred in the battery (the 8th lithium battery) that does not add flame-retardant additive.In the test of directly burning under this type intense environment; Adopt the battery (first lithium battery to the, seven lithium batteries) of method preparation of the present invention; That flame-retardant additive is added in the battery (the 9th and the tenth lithium battery) of method preparation of a fluid injection in the electrolyte is the same with adopting directly; The phenomenon of smoldering all only occurs, do not take place on fire or blast, do not add battery (the 8th lithium battery) phenomenon that then an explosion occurred of flame-retardant additive.Above test result shows, adopts method of the present invention to prepare battery, owing to be added with flame-retardant additive, the fail safe that has improved battery greatly.
The volume test of battery:
Under the normal temperature, adopt BS-9300 (R) secondary cell Performance Detection cabinet, charging modes is that constant current constant voltage is to 4.2V; Discharge mode is that constant-current discharge is to 3.1V; Charging and discharging currents is 1C, respectively records every kind of prepared capability value that gets nine kinds of batteries of method, make even all back result such as table 2.
Table 2: the volume test table of battery
Volume test result by table 2 can know; Adopt method prepared cell of the present invention; Owing to adopt the back to add the method for flame-retardant additive; Battery formed SEI film when changing into is more stable, makes that the capacity of battery is the same with not adding the battery of flame-retardant additive, and all the capacity than the battery (the 9th lithium battery and the tenth lithium battery) that adopts the direct method preparation that flame-retardant additive is added in a fluid injection in the electrolyte is high.
The multiplying power discharging volume test of battery:
Adopt BK6016 type secondary cell Performance Detection cabinet, above-mentioned ten kinds of batteries have been carried out the multiplying power discharging volume test, method of testing is: elder generation, shelved 10 minutes to 4.2V with 1C (800mA) constant voltage charge; Be discharged to 3.0V with 5C then, shelved 10 minutes, be discharged to 3.0V, shelved 10 minutes with 4C; Be discharged to 3.0V with 3C then, shelved 10 minutes, be discharged to 3.0V with 2C then; Shelved 10 minutes, and be discharged to 3.0V with 1C then, shelved 10 minutes; Be discharged to 3.0V with 0.5C then, shelved 10 minutes, be discharged to 3.0V with 0.2C then.The ratio of the discharge capacity of the discharge capacity when writing down current discharge with 5C, 4C, 3C, 2C, 1C, 0.5C and 0.2C respectively with the time with the current discharge of 0.2C to 3.0V, data are as shown in table 3:
Table 3: the multiplying power discharging volume test of battery
Can be known by table 3, adopt first to the 7th made lithium battery of method of the present invention, its high rate performance is suitable with the high rate performance of the 8th lithium battery that does not add flame-retardant additive, all is higher than the 9th lithium battery and the tenth lithium battery.This also is that when changing into formation SEI film, owing to there is not the existence of flame-retardant additive, formed SEI film is identical with the composition of the SEI film of the battery that does not add flame-retardant additive, thereby makes that its high rate performance is suitable owing to adopt the made battery of method of the present invention.And employing directly is added in flame-retardant additive the battery (the 9th and the tenth lithium battery) of the method preparation of a fluid injection in the electrolyte; Because the effect of flame-retardant additive is arranged when forming the SEI film; Make the SEI film component that forms that variation take place, thereby the high rate performance of battery descend.
The cycle performance test of battery:
To adopt above-mentioned ten kinds of lithium ion batteries to carry out the cycle performance test; Method of testing is: adopt BS-9300 type lithium ion battery performance test cabinet, elder generation, shelved 5 minutes to 4.2V with the 1C constant-current constant-voltage charging; Be discharged to 3.0V with 1C; Again with the 1C constant-current constant-voltage charging to 4.2V, the capacity, discharge attitude internal resistance, middle threshold voltage of each circulation etc. are write down in circulation like this.After the loop ends, treat battery recovery normal temperature, be full of electricity, be discharged to 3.0V with 0.2C again, draw residual capacity, residual capacity is promptly got the circulation volume surplus ratio divided by circulation volume first with 1C.The gained result is as shown in table 4:
Table 4: the cycle performance test chart of battery
Can find out by table 4; Adopt the made battery of method of the present invention; Its cycle performance is suitable with the cycle performance of battery (the 8th lithium battery) that does not add flame-retardant additive, all obviously is superior to adopting directly the cycle performance of battery (the 9th and the tenth lithium battery) that flame-retardant additive is added in the method preparation of a fluid injection in the electrolyte.This is that employing adds flame-retardant additive in the electrolyte earlier when making owing to the 9th and the tenth lithium battery; Injecting battery then together changes into; Can not well protect electrolyte by less stable owing to the influence of flame-retardant additive for formed like this SEI film, in the cyclic process of battery; Electrolyte component can continue to be reduced, thereby causes the decline of cycle performance of battery.And adopt method of the present invention to prepare battery; Because when forming the SEI film; Flame-retardant additive does not also add, and the composition of at this moment formed SEI film and performance and the SEI film when not adding flame-retardant additive are basic identical, so yet suitable excellence of its cycle performance.
More than the manufacture method of the battery that the embodiment of the invention provided has been carried out detailed introduction; Used concrete example among this paper principle of the present invention and execution mode are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, the part that on embodiment and range of application, all can change, in sum, this description should not be construed as limitation of the present invention.
Claims (11)
1. the manufacture method of a battery is characterized in that, comprising:
Electrolyte is injected into through the liquid injection port on the battery case carries out opening in the battery case and change into;
When the negative terminal surface of battery through described opening change into form stable solid electrolyte interface film after, add flame-retardant additive;
Seal said liquid injection port.
2. the manufacture method of battery according to claim 1 is characterized in that, after said negative terminal surface when battery forms stable solid electrolyte interface film, adds after the flame-retardant additive, and before sealing said liquid injection port, said method also comprises:
Carry out the ageing operation, to detect the performance of battery.
3. the manufacture method of battery according to claim 1 and 2; It is characterized in that said flame-retardant additive is a trimethyl phosphate, triethyl phosphate; Triethyl phosphite; The trifluoroethyl phosphate, six-trifluoroethyl tripolyphosphazene, a kind of or both perhaps many persons' the combinations arbitrarily in the perfluoro diethyl ether.
4. the manufacture method of battery according to claim 3 is characterized in that, said flame-retardant additive is 1%～50% with respect to the weight percentage of electrolyte quality.
5. the manufacture method of battery according to claim 4 is characterized in that, said flame-retardant additive is 10%～40% with respect to the weight percentage of electrolyte quality.
6. the manufacture method of battery according to claim 1 and 2 is characterized in that, said flame-retardant additive is a trimethyl phosphate, and said trimethyl phosphate is 10%～30% with respect to the weight percentage of electrolyte quality.
7. the manufacture method of battery according to claim 1 and 2 is characterized in that, said flame-retardant additive is a triethyl phosphate, and said triethyl phosphate is 20% with respect to the weight percentage of electrolyte quality.
8. the manufacture method of battery according to claim 1 and 2 is characterized in that, said flame-retardant additive is a triethyl phosphite, and said triethyl phosphite is 20% with respect to the weight percentage of electrolyte quality.
9. the manufacture method of battery according to claim 1 and 2 is characterized in that, said flame-retardant additive is the trifluoroethyl phosphate, and said trifluoroethyl phosphate is 20% with respect to the weight percentage of electrolyte quality.
10. the manufacture method of battery according to claim 1 and 2 is characterized in that, when said flame-retardant additive was six-trifluoroethyl tripolyphosphazene, said six-trifluoroethyl tripolyphosphazene was 10% with respect to the weight percentage of electrolyte quality.
11. the manufacture method of battery according to claim 1 and 2 is characterized in that, said flame-retardant additive is the perfluoro diethyl ether, and said perfluoro diethyl ether is 30% with respect to the weight percentage of electrolyte quality.
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