CN107546358A - One kind fluorination barrier film ultralow temperature lithium battery - Google Patents
One kind fluorination barrier film ultralow temperature lithium battery Download PDFInfo
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- CN107546358A CN107546358A CN201710756519.6A CN201710756519A CN107546358A CN 107546358 A CN107546358 A CN 107546358A CN 201710756519 A CN201710756519 A CN 201710756519A CN 107546358 A CN107546358 A CN 107546358A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention provides a kind of fluorination barrier film ultralow temperature lithium battery, and the lithium battery includes shell and positive pole, negative pole, barrier film and electrolyte in shell；The barrier film is located between positive pole and negative pole；Electrolyte is filled in shell；The barrier film is fluorination barrier film, specifically by the porous polyvinyl fluoride barrier film obtained after porous polyethylene diaphragm matrix, the fluorination of porous polypropylene diaphragm matrix or porous poly- fluoropropene barrier film.The lithium battery of the present invention is by using fluorination barrier film, and to being improved to the active material of positive pole and negative pole, it can realize that 40 DEG C remain to possess good discharge performance, the manufacture and use in new-energy automobile power battery can be applied well, and the development to promotion new-energy automobile is significant.
Description
Technical field
The present invention relates to a kind of lithium battery, and in particular to a kind of ultralow temperature lithium battery, more particularly to it is a kind of using fluorination every
The ultralow temperature lithium battery of film.
Background technology
Lithium battery (Lithium battery) refer in electrochemical system containing lithium (including lithium metal, lithium alloy and lithium from
Son, lighium polymer) battery.Lithium battery is broadly divided into two classes：Lithium metal battery and lithium ion battery.Lithium metal battery is usual
It is non-rechargeabel, and includes the lithium of metallic state.Lithium ion battery does not contain the lithium of metallic state, and can charge.This
The lithium battery referred in invention refers to lithium ion battery.
Lithium battery has been widely used for various fields as green novel energy source, but its cryogenic property is poor, particularly-
Service behaviour in less than 30 DEG C low temperature environments is poor, makes its application and aviation boat on wearing product, automobile lithium battery
The application of the special dimension such as it and military affairs is by many limitations.Metaphor is said：New energy in the Northeast of China or Russia
Lithium battery on automobile, if not solving the problems, such as the low temperature resistant of lithium battery, new-energy automobile can not just start in winter, more not
Say can also travel how far.And the conventional lithium battery on existing domestic market typically at -10 DEG C cannot normal work, some factories
The lithium battery of family's production just can not put electricity at all at -5 DEG C.
New-energy automobile if it is desired to really realize tested with conventional gasoline car body it is close, shorten the charging interval, improve continue a journey in
Journey and the convenience of charging are unavoidable topics.
Existing lithium battery includes positive pole, negative pole, electrolyte, barrier film, and lithium battery temperature characterisitic is except the structure with battery
Outside design, electrical conductivity, electrode material granules degree, preparation technology and electrolyte etc. are relevant, also with used positive and negative pole material,
Diaphragm material is relevant.The difference of positive and negative pole material, the cryogenic property of lithium battery also differ；The organic electrolyte that lithium battery uses
Liquid, such as grease, it can become sticky at low temperature or even condense so that the activity of conductive lithium salts inside is limited significantly
System, such words charge efficiency is very low, so as to which lithium battery can be caused to charge at low temperature slowly, is not fully filled, and electric discharge is also such.
In addition, in the structure of lithium battery, barrier film is one of crucial interior layer assembly.The performance of barrier film determines the boundary of battery
Face structure, internal resistance etc., the characteristics such as capacity, circulation and the security performance of battery are directly affected, the barrier film of excellent performance is to improving
The combination property of battery has the function that important.The main function of barrier film is that the positive and negative electrode for making battery is separated, and prevents the two poles of the earth
Contact and it is short-circuit, additionally with the function that electrolyte ion passes through can be made.Barrier film material is nonconducting, its physical chemistry
The performance of confrontation battery has a great impact.The species of battery is different, and the barrier film of use is also different.It is serial for lithium battery, by
It is organic solvent system in electrolyte, thus needs the diaphragm material of organic solvent-resistant, it is general using high-strength thin-film
Polyolefin porous membrane.But the heat endurance of traditional polyalkene diaphragm is poor, the safety and low temperature of lithium battery can not be ensured
Under for lithium battery cycle performance.
Documents 1：A kind of open improvement of CN2016101846435 (nonaqueous electrolytic solution and the lithium ion battery for including it)
The lithium ion battery of electrolyte, by using cyclic sulfates class compound and sodium salt to be used as additive in the electrolytic solution, improve
The high temperature cyclic performance of lithium ion battery, while can also be under -10 DEG C of temperature conditionss, 0.5C is discharged to 3.0V, its electricity that discharges
Capacity can reach the 78.37% of normal temperature discharge capacity.
Documents 2:CN2014103742643 (lithium ion battery and its electrolyte) and a kind of open improvement electrolyte
Lithium ion battery, by adding fluorinated ethylene carbonate in the electrolytic solution so that temperature conditionss of the lithium battery at -10 DEG C
Under, 0.5C is discharged to 3.0V, and its discharge capacity can reach the 95% of normal temperature discharge capacity, but it is in lower temperature condition
Under can not discharge.
Above-mentioned two parts of documents, are all to improve the low temperature performance of lithium ion battery by improving electrolyte.
Documents 3：CN106876778A discloses a kind of lithium rechargeable battery, and it can be under -20 DEG C of cryogenic conditions
Still there is preferable discharge performance, while there can also be preferable charging performance at normal temperatures.
The lithium ion battery that above-mentioned documents provide can not all realize the electric discharge of more low temperature, and its application has certain ring
Border limitation.
The present invention intends providing one kind by improving diaphragm material and both positive and negative polarity active material, to improve the low of lithium ion battery
Warm discharge performance, can realize still has the ultralow temperature lithium battery of preferable discharge performance under -40 DEG C of cryogenic conditions；The ultralow temperature lithium
The development studied successfully to promotion new-energy automobile of battery is significant.
The content of the invention
The technical problem to be solved in the present invention is to provide still have preferable electric discharge under a kind of cryogenic conditions that can realize -40 DEG C
The ultralow temperature lithium battery of performance.
In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：
There is provided a kind of fluorination barrier film ultralow temperature lithium battery, the lithium battery includes shell and positive pole in shell, negative
Pole, barrier film and electrolyte；The barrier film is located between positive pole and negative pole；Electrolyte is filled in shell；
The barrier film is fluorination barrier film, is specifically fluorinated porous polyethylene diaphragm matrix, porous polypropylene diaphragm matrix
The porous polyvinyl fluoride barrier film or porous poly- fluoropropene barrier film obtained afterwards.
Further,
The preparation method of the fluorination barrier film, is in F2 by porous polyethylene diaphragm matrix or porous polypropylene diaphragm matrix
Fluorination obtains porous polyvinyl fluoride barrier film in the presence of gas or porous poly- fluoropropene barrier film, fluorination conditions are as follows：
It is fluorinated pressure：0.1-0.3Mpa；It is fluorinated temperature：50-80℃；It is fluorinated the time：1-1.5h.
Further,
Positive electrode active materials include the component of following mass fraction used by the positive pole：
Cobalt acid lithium 87.5-96.5%, conductive carbon black 0.5-4.55%, electrically conductive graphite 1-6.5%, graphene 0.1-1.5%,
CNT 0.05-1%, Kynoar 0.5-4.5%, N-methyl is than pyrrolidone 0.5-1.5%, the 0.5- of antifreezing agent one
1.5%.
Further,
Negative active core-shell material includes the component of following mass fraction used by the negative pole：
Graphite 85-92.5%, butadiene-styrene rubber 1.5-3.5%, sodium carboxymethylcellulose 0.3-4.6%, electrically conductive graphite 1-
3.5%, graphene 0.2-2.5%, deionized water 3.5-4.5%, vinylene carbonate fat 0.12-0.8%, the 0.5- of antifreezing agent two
1.5%.
Further,
The antifreezing agent one is glycerine, one kind in triethanolamine or combination.
Further,
The antifreezing agent two is glycerine, one kind in triethanolamine or combination.
Further,
The electrolyte is LiF6PO4 organic solutions.
Further,
The lithium battery also includes anode ear and negative electrode lug, and one end of the anode ear mutually connects with positive pole, anode ear
The other end manifests shell；One end of the negative electrode lug mutually connects with negative pole, and the other end of negative electrode lug manifests shell.
Further,
The shell includes upper and lower two layers of aluminium foil layer and middle nylon layer, is connected between each layer by adhesive layer.
Further,
The lithium battery also includes being arranged on shell and anode ear, the insulating trip one of negative electrode lug junction, insulating trip two.
The present invention be separately added into positive electrode active materials and negative active core-shell material antifreezing agent (glycerine, triethanolamine or
It is combined), it is low using glycerine and triethanolamine freezing point, and the principle with organic electrolyte similar compatibility so that electrolyte
It will not solidify at low ambient temperatures, the work so that lithium ion battery of the present invention can also can discharge at low ambient temperatures.
Because the fluorine atom in fluoride is the atom that electronegativity is maximum in nature all elements and polarizability is minimum,
It is very active chemical element, ion or common fluorine compounds can be formed with most of element.The present invention is by poly- second
Alkene barrier film or polypropylene diaphragm are fluorinated, and fluorination barrier film are formed, to improve the properties of barrier film.Because c h bond can be
414.2kJ/mol, C-F bond energy are 444.1kJ/mol, and the bond energy of carbon-fluorine bond is bigger than C-H bond bond energy, and activity is high, and stability is strong.
The polyethylene diagrams or polypropylene diaphragm being fluorinated, because the H groups of itself are substituted by F groups, obtain fluorination barrier film on-F
Group polarity is very big so that the polarity enhancing of the barrier film after fluorination, strengthens with the affinity of polarity electrolyte, so that every
Guarantor's liquid measure increase of film.It is easy to and the CMC (carboxymethyl celluloses on the PVDF (Kynoar) and negative pole on positive pole simultaneously
Sodium) coordinate bond is formed, along with interatomic Van der Waals force so that the bonding force of barrier film and pole piece increases, and the hardness of battery core increases
By force.Polyethylene diagrams or polypropylene diaphragm after fluorination also have an obvious advantage, are exactly that its heat-shrinkable is more preferable, certain
Security performance, the enhancing electric conductivity of battery core can be improved in degree.
The present invention can improve the security of lithium ion using fluorination barrier film；Increase the low-temperature conductive performance of lithium battery；Improve
The service life of lithium battery；Increase the cycle-index of lithium battery；The heat endurance of improvement lithium battery and oneself for improving lithium battery
Discharge performance.
The lithium battery of the present invention, can and to being improved to the active material of positive pole and negative pole by using fluorination barrier film
With realize -40 DEG C remain to possess good discharge performance, can apply well new-energy automobile power battery manufacture and make
With the development to promotion new-energy automobile is significant.It is important so as to also have because lithium battery is a kind of green energy resource
Energy-conserving and environment-protective effect.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the discharge curve of the 1# samples of the embodiment of the present invention 1；
Fig. 2 is the discharge curve of the 2# samples of the embodiment of the present invention 2；
Fig. 3 is the discharge curve of the 3# samples of the embodiment of the present invention 3；
Fig. 4 is the structural representation of the embodiment of the present invention；
Above-mentioned reference：
1A is the 1C discharge curves of 1# samples；1B is the 0.2C discharge curves of 1# samples；1C is that the 0.5C of 3# samples discharges
Curve；
2A is the 1C discharge curves of 2# samples；2B is the 0.2C discharge curves of 2# samples；2C is that the 0.5C of 2# samples discharges
Curve；
3A is the 1C discharge curves of 3# samples；3B is the 0.2C discharge curves of 3# samples；3C is that the 0.5C of 3# samples discharges
Curve；
Shell 1；Positive pole 2；Negative pole 3；Barrier film 4；Anode ear 51；Negative electrode lug 52；Insulating trip 1；Insulating trip 2 62.
Embodiment
Below in conjunction with the accompanying drawings and embodiment the present invention is further described, but be not limited to the scope of the present invention.
Embodiment 1：
As Figure 1-4, the present invention provides a kind of fluorination barrier film ultralow temperature lithium battery, and the lithium battery includes shell and set
In the positive pole 2 in shell 1, negative pole 3, barrier film 4 and electrolyte；Barrier film 4 is located between positive pole 2 and negative pole 3；Electrolyte is filled in outer
In shell；
The lithium battery also includes anode ear 51 and negative electrode lug 52, and one end and the phase of positive pole 2 of anode ear 51 connect, anode ear
51 other end manifests shell 1；One end of negative electrode lug 52 connects with the phase of negative pole 3, and the other end of negative electrode lug 52 manifests shell
1。
Shell 1 includes upper and lower two layers of aluminium foil layer and middle nylon layer, is connected between each layer by adhesive layer.
Insulating trip 1, the insulating trip that the lithium battery is set respectively in shell 1 and anode ear 51, the junction of negative electrode lug 52
2 62.
Barrier film 4 is porous polyethylene barrier film, and the porous polyethylene barrier film is by by porous polyethylene diaphragm matrix
It is fluorinated and is made in the presence of F2 gases, fluorination conditions is as follows：It is fluorinated pressure：0.1Mpa；It is fluorinated temperature：50℃；It is fluorinated the time：
1.5h。
Positive electrode active materials include the component of following mass fraction used by positive pole 2：
Cobalt acid lithium 87.5%, conductive carbon black 4.35%, electrically conductive graphite 6.5%, graphene 0.1%, CNT 0.05%,
Kynoar 0.5%, N-methyl is than pyrrolidone 0.5%, antifreezing agent one 0.5%.The antifreezing agent one is glycerine.
Negative active core-shell material includes the component of following mass fraction used by negative pole 3：
Graphite 85%, butadiene-styrene rubber 3.5%, sodium carboxymethylcellulose 4.5%, electrically conductive graphite 1%, graphene 0.2%, go
Ionized water 3.5%, vinylene carbonate fat 0.8%, antifreezing agent 2 1.5%.The antifreezing agent two is glycerine.
The electrolyte is LiF6PO4 organic solutions.
Lithium battery sample is designated as 1# samples made from the present embodiment, carries out low temperature performance test under the following conditions：
Test environment conditions：23 DEG C ± 2 DEG C of environment temperature, ambient humidity：56-60%；Test equipment：Rechargeable battery is examined
Measurement equipment (BK-6816AR/3) JCZX-EQ-056；High-low temperature test chamber (WGD701) JCZX-EQ-002.
Method of testing：
1st, at 23 DEG C ± 2 DEG C of room temperature, battery is with 0.51ItA constant-current constant-voltage chargings to 3.7V, cut-off current 0.02ItA；
2nd, battery stands 4h in the environment of -40 DEG C；
3rd, battery with 0.5ItA constant-current discharges to 2.5V, records discharge capacity under -40 DEG C of environment.
After tested, measure at -40 DEG C, 1C, 0.5C, 0.2C discharge data are as follows：
- 40 DEG C of discharge datas of the 1# sample lithium batteries of table 1
The discharge curve of the present embodiment 1# sample lithium batteries is as shown in Figure 1.
Embodiment 2：
The present embodiment and the difference of embodiment 1 are：
Barrier film 4 is porous poly- fluoropropene barrier film, and the preparation method of the porous poly- fluoropropene barrier film is by porous polypropylene
Diaphragm matrix is fluorinated in the presence of F2 gases to be made, and fluorination conditions are as follows：It is fluorinated pressure：0.3Mpa；It is fluorinated temperature：80℃；
It is fluorinated the time：1h.
Positive electrode active materials include the component of following mass fraction used by positive pole 2：
Cobalt acid lithium 96.5%, conductive carbon black 0.5%, electrically conductive graphite 1%, graphene 0.1%, CNT 0.4%, gather inclined
PVF 0.5-4.5%, N-methyl is than pyrrolidone 0.5%, antifreezing agent one 0.5%.The antifreezing agent one is triethanolamine.
Negative active core-shell material includes the component of following mass fraction used by negative pole 3：
Graphite 92.5%, butadiene-styrene rubber 1.5%, sodium carboxymethylcellulose 0.3%, electrically conductive graphite 1%, graphene 0.2%,
Deionized water 3.5%, vinylene carbonate fat 0.5%, antifreezing agent 2 0.5.The antifreezing agent two is triethanolamine.
Lithium battery sample is designated as 2# samples made from the present embodiment, using method of testing same as Example 1 and test
Condition carries out low temperature performance test, after tested, measures at -40 DEG C, 1C, 0.5C, 0.2C discharge data are as follows：
- 40 DEG C of discharge datas of the 2# sample lithium batteries of table 2
The discharge curve of the present embodiment 2# sample lithium batteries is as shown in Figure 2.
Embodiment 3：
The present embodiment and the difference of embodiment 1 are：
Barrier film 4 is porous polyethylene barrier film, and the porous polyethylene barrier film is by by porous polyethylene diaphragm matrix
It is fluorinated and is made in the presence of F2 gases, fluorination conditions is as follows：It is fluorinated pressure：0.2Mpa；It is fluorinated temperature：65℃；It is fluorinated the time：
1.2h。
Positive electrode active materials include the component of following mass fraction used by positive pole 2：
Cobalt acid lithium 89%, conductive carbon black 4.55%, electrically conductive graphite 2.5%, graphene 1%, CNT 0.35%, gather inclined
PVF 0.6%, N-methyl is than pyrrolidone 1%, antifreezing agent one 1%.The antifreezing agent one is glycerine, the group of triethanolamine
Close, glycerine, triethanolamine are respectively 50%.
Negative active core-shell material includes the component of following mass fraction used by negative pole 3：
Graphite 86%, butadiene-styrene rubber 2%, sodium carboxymethylcellulose 4.6%, electrically conductive graphite 1.5%, graphene 0.78%,
Deionized water 4%, vinylene carbonate fat 0.12%, antifreezing agent 2 1%.The antifreezing agent two is glycerine, the group of triethanolamine
Close, glycerine, triethanolamine are respectively 50%.
Lithium battery sample is designated as 3# samples made from the present embodiment, using method of testing same as Example 1 and test
Condition carries out low temperature performance test, after tested, measures at -40 DEG C, 1C, 0.5C, 0.2C discharge data are as follows：
- 40 DEG C of discharge datas of the 3# sample lithium batteries of table 3
The discharge curve of the present embodiment 3# sample lithium batteries is as shown in Figure 3.
Interpretation of result：
The lithium battery 1-3# samples provided by 1-3 of the embodiment of the present invention can in -40 DEG C of discharge data and discharge curve
To learn, 1-3# samples still have good discharge performance at -40 DEG C.
Accordingly, it is capable to the manufacture and use in new-energy automobile power battery are applied well, to promoting new-energy automobile
Develop significant.Because lithium battery is a kind of green energy resource, so as to also have important energy-conserving and environment-protective to act on.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent defines.
Claims (10)
1. one kind fluorination barrier film ultralow temperature lithium battery, it is characterised in that
The lithium battery includes shell and positive pole, negative pole, barrier film and electrolyte in shell；The barrier film located at positive pole with
Between negative pole；Electrolyte is filled in shell；
The barrier film is fluorination barrier film, will specifically be obtained after porous polyethylene diaphragm matrix, the fluorination of porous polypropylene diaphragm matrix
The porous polyvinyl fluoride barrier film or porous poly- fluoropropene barrier film arrived.
A kind of 2. fluorination barrier film ultralow temperature lithium battery according to claim 1, it is characterised in that
The preparation method of the fluorination barrier film, is in F2 gases by porous polyethylene diaphragm matrix or porous polypropylene diaphragm matrix
In the presence of fluorination obtain porous polyvinyl fluoride barrier film or porous poly- fluoropropene barrier film, fluorination conditions are as follows：
It is fluorinated pressure：0.1-0.3Mpa；It is fluorinated temperature：50-80℃；It is fluorinated the time：1-1.5h.
A kind of 3. fluorination barrier film ultralow temperature lithium battery according to claim 1, it is characterised in that
Positive electrode active materials include the component of following mass fraction used by the positive pole：
Cobalt acid lithium 87.5-96.5%, conductive carbon black 0.5-4.55%, electrically conductive graphite 1-6.5%, graphene 0.1-1.5%, carbon are received
Mitron 0.05-1%, Kynoar 0.5-4.5%, N-methyl is than pyrrolidone 0.5-1.5%, the 0.5-1.5% of antifreezing agent one.
A kind of 4. fluorination barrier film ultralow temperature lithium battery according to claim 1, it is characterised in that
Negative active core-shell material includes the component of following mass fraction used by the negative pole：
Graphite 85-92.5%, butadiene-styrene rubber 1.5-3.5%, sodium carboxymethylcellulose 0.3-4.6%, electrically conductive graphite 1-3.5%,
Graphene 0.2-2.5%, deionized water 3.5-4.5%, vinylene carbonate fat 0.12-0.8%, the 0.5-1.5% of antifreezing agent two.
A kind of 5. fluorination barrier film ultralow temperature lithium battery according to claim 3, it is characterised in that
The antifreezing agent one is glycerine, one kind in triethanolamine or combination.
A kind of 6. fluorination barrier film ultralow temperature lithium battery according to claim 4, it is characterised in that
The antifreezing agent two is glycerine, one kind in triethanolamine or combination.
A kind of 7. fluorination barrier film ultralow temperature lithium battery according to claim 1, it is characterised in that
The electrolyte is LiF6PO4 organic solutions.
A kind of 8. fluorination barrier film ultralow temperature lithium battery according to claim 1, it is characterised in that
The lithium battery also includes anode ear and negative electrode lug, and one end of the anode ear mutually connects with positive pole, anode ear it is another
End manifests shell；One end of the negative electrode lug mutually connects with negative pole, and the other end of negative electrode lug manifests shell.
A kind of 9. fluorination barrier film ultralow temperature lithium battery according to claim 1, it is characterised in that
The shell includes upper and lower two layers of aluminium foil layer and middle nylon layer, is connected between each layer by adhesive layer.
A kind of 10. fluorination barrier film ultralow temperature lithium battery according to claim 8, it is characterised in that
The lithium battery also includes being arranged on shell and anode ear, the insulating trip one of negative electrode lug junction, insulating trip two.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111224102A (en) * | 2020-01-10 | 2020-06-02 | 江西远东电池有限公司 | Preparation method of low-temperature battery |
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| CN1599095A (en) * | 2003-09-17 | 2005-03-23 | 大和纺织株式会社 | Separator for battery and manufacturing method thereof |
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