CN103280597A - Lithium ion battery - Google Patents
Lithium ion battery Download PDFInfo
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- CN103280597A CN103280597A CN2013102137343A CN201310213734A CN103280597A CN 103280597 A CN103280597 A CN 103280597A CN 2013102137343 A CN2013102137343 A CN 2013102137343A CN 201310213734 A CN201310213734 A CN 201310213734A CN 103280597 A CN103280597 A CN 103280597A
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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
Abstract
The invention discloses a lithium ion battery which comprises a positive plate, a negative plate and an isolating membrane spaced between the positive plate and the negative plate, wherein the positive plate comprises a positive current collector and a positive membrane coated on the positive current collector; the negative plate comprises a negative current collector and a negative membrane coated on the negative current collector; the partial area of the positive current collector or the negative current collector is coated with a low-melting-point coating, and the part, corresponding to the low-melting-point coating, of the other current collector is coated with a conductive resistance layer; and the parts, corresponding to the low-melting-point coating and the conductive resistance layer, of the isolating membrane are provided with holes, so that the low-melting-point coating is in direct contact with the conductive resistance layer. Compared with the prior art, the lithium ion battery disclosed by the invention has the advantages that overcharge protection of the battery is realized by a physical short-circuit method, and not only is the safety of the battery at an overcharge state ensured, but also large influence on the electrochemical property of the battery can be avoided.
Description
Technical field
The invention belongs to the lithium ion battery field, more particularly, the present invention relates to a kind of lithium ion battery with good over-charge protective performance.
Background technology
Lithium ion battery is since commercialization, owing to plurality of advantages such as it has energy density height, operating voltage height, memory-less effect, has extended cycle life, environmentally safe are widely used as the power supply of various mobile devices, thereby entered the large-scale practical stage rapidly.
Along with the continuous multifunction of various mancarried electronic aids with become more meticulous, its energy density to lithium ion battery has also proposed more and more higher requirement, and the raising of lithium ion battery energy density then designs safely it and has higher requirement.Because battery can lasting heat release, especially active material of cathode and electrolyte etc. also can side reaction occur and a large amount of heat release when battery arrives high voltage in the process of overcharging, after thermal accumlation arrived to a certain degree, just there was the risk of combustion explosion in battery.Happening occasionally of battery of mobile phone exploding and firing accident illustrated that the security performance of existing battery also existed great hidden danger in recent years.
In view of this, necessaryly provide a kind of lithium ion battery with good over-charge protective performance.
Summary of the invention
The objective of the invention is to: a kind of lithium ion battery with good over-charge protective performance is provided.
In order to realize the foregoing invention purpose, the invention provides a kind of lithium ion battery, it comprises positive plate, negative plate and be interval in barrier film between the positive/negative plate, positive plate comprises plus plate current-collecting body and the anodal diaphragm of coating on the plus plate current-collecting body, negative plate comprises negative current collector and the cathode membrane of coating on the negative current collector, subregion on plus plate current-collecting body or the negative current collector is coated with one deck low melting point coating, the position corresponding with the low melting point coating is coated with one deck conductive resistance layer on another collector, barrier film with the low melting point coating, the corresponding position of conductive resistance layer offers perforate and the low melting point coating directly contacted with the conductive resistance layer.
When lithium ion battery of the present invention because of overcharge be warmed up to uniform temperature after, its low melting point coating namely is melted, and makes positive/negative plate form short dot at the barrier film tapping, thereby plays the effect of shunting; Simultaneously, the conductive resistance layer of coating can reduce the electric current that internal short-circuit produces, and reduces heat release.Because the size of electric current in the time of can controlling short circuit by the resistance of control conductive resistance layer, therefore final charging current can be passed through from internal short-circuit point, thereby avoids the battery combustion explosion, guarantees the fail safe of battery under the state of overcharging.
A kind of improvement as lithium ion battery of the present invention, the fusing point of described low melting point coating is between 60 ℃ to 200 ℃, its reason is: if the fusing point of low melting point coating is too high, just can't fusing causes internal short-circuit before the battery burning, thereby not have the protective effect to battery; If the fusing point of low melting point coating is too low, can cause battery short circuit at high temperature to be lost efficacy again.
As a kind of improvement of lithium ion battery of the present invention, between the 200 μ m, its reason is the thickness of described low melting point coating at 5 μ m: if the thickness of low melting point coating is too little, the normal use of battery also has short-circuit risks down; If the thickness of low melting point coating is too big, then can influence the possibility of short circuit under the energy density of battery and the high temperature.
A kind of improvement as lithium ion battery of the present invention, described low melting point coating is the coating that is insoluble to electrolyte, its swellbility in electrolyte is less than 100%, and its reason is: if the low melting point coating is dissolved in electrolyte, then battery namely can be short-circuited in the course of processing and lose efficacy; If the swellbility of low melting point coating is too big, then battery has short-circuit risks.
As a kind of improvement of lithium ion battery of the present invention, described low melting point coating is a kind of or its combination in paraffin, Witcodur 272, Ployethylene Wax, the polypropylene.
A kind of improvement as lithium ion battery of the present invention, the resistivity of described conductive resistance layer at 0.5 Ω/m between 200 Ω/m, its reason is: if the resistivity of conductive resistance layer is too low, can cause the electric current that produces behind the over-charging of battery high temperature internal short-circuit too big, its excessive heat release also may cause the battery burning; If the resistivity of conductive resistance layer is too high, does not then have the effect of shunting and can't form effective protection to battery.
As a kind of improvement of lithium ion battery of the present invention, the thickness of described conductive resistance layer at 5 μ m between the 200 μ m.
As a kind of improvement of lithium ion battery of the present invention, the perforate size of described barrier film account for plane, perforate place place on the volume core cross-sectional area 5%～100%, this is too little and reduce the possibility of high temperature short circuit for fear of the barrier film perforate.
As a kind of improvement of lithium ion battery of the present invention, described conductive resistance layer forms by the slurry coating that contains butylbenzene binding agent, sodium carboxymethylcellulose and conductive black.
As a kind of improvement of lithium ion battery of the present invention, described lithium ion battery is the winding type lithium ion battery, and low melting point coating and conductive resistance layer are coated on the coiling initiating terminal of positive/negative plate or finish end.
Compared with prior art, the present invention adopts the method for physics short circuit to realize the over-charge protective of battery, has both effectively guaranteed the safety of battery under the state of overcharging, and can not produce big influence to the chemical property of battery again.
Description of drawings
Below in conjunction with the drawings and specific embodiments, lithium ion battery of the present invention and beneficial effect thereof are elaborated, wherein:
Fig. 1 is the structural representation of lithium ion battery first execution mode of the present invention.
Fig. 2 is the structural representation of lithium ion battery second execution mode of the present invention.
Fig. 3 is the barrier film perforate schematic diagram of lithium ion battery of the present invention.
The lithium ion battery that Fig. 4 makes for Comparative Examples 1 overcharges electric current and voltage temperature time history plot in the process at 1C6V.
The lithium ion battery that Fig. 5 makes for Comparative Examples 2 overcharges electric current and voltage temperature time history plot in the process at 1C6V.
The lithium ion battery that Fig. 6 makes for embodiment 1 overcharges electric current and voltage temperature time history plot in the process at 1C6V.
Embodiment
In order to make goal of the invention of the present invention, technical scheme and useful technique effect more clear, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be understood that the embodiment that describes in this specification only is in order to explain the present invention, is not in order to limit the present invention.
See also Fig. 1 to Fig. 3, lithium ion battery of the present invention comprises positive plate 10, negative plate 20 and barrier film 30.Positive plate 10 comprises plus plate current-collecting body 12 and the anodal diaphragm of coating on the plus plate current-collecting body 12 14, and negative plate 20 comprises negative current collector 22 and the cathode membrane of coating on the negative current collector 22 24.Barrier film 30 is interval between positive plate 10 and the negative plate 20.
Wherein, subregion on the plus plate current-collecting body 12 is coated with one deck low melting point coating 40, position corresponding with low melting point coating 40 on the negative current collector 22 is coated with one deck conductive resistance layer 50,30 of barrier films with low melting point coating 40, conductive resistance layer 50 correspondence position offer perforate 32, the existence of perforate 32 makes low melting point coating 40 directly contact with conductive resistance layer 50.The size of perforate 32 is about 50% of low melting point coating 40 spreading areas, and corresponding with the centre position of low melting point coating 40.
In different execution modes, low melting point coating 40 and conductive resistance layer 50 can be coated on the coiling initiating terminal of positive plate 10 and negative plate 20 as shown in Figure 1 respectively, and the coiling that also can be coated on positive plate 10 and negative plate 20 as shown in Figure 2 respectively finishes end.
In addition, the pole piece that low melting point coating 40 and conductive resistance layer 50 are coated with can exchange, and that is to say, low melting point coating 40 can also be coated on the negative current collector 22, simultaneously conductive resistance layer 50 is coated on the correspondence position of plus plate current-collecting body 12.
When lithium ion battery of the present invention because of overcharge be warmed up to uniform temperature after, its low melting point coating 40 namely is melted, positive/negative plate forms short dot at perforate 32 places of barrier film 30, thereby plays the effect of shunting; Simultaneously, the conductive resistance layer 50 of coating can reduce the electric current that internal short-circuit produces, and reduces heat release.Because the size of electric current in the time of can controlling short circuit by the resistance of control conductive resistance layer 50, therefore final charging current can be passed through from internal short-circuit point, thereby avoids the battery combustion explosion, guarantees the fail safe of battery under the state of overcharging.
The preparation of negative plate: the cathode size prescription is pressed the siccative weight percent meter, by 2% butylbenzene binding agent, 2% sodium carboxymethylcellulose, 1.5% conductive black, 94.5% negative electrode active material totally four parts form, wherein negative electrode active material adopts Delanium.At first, by above prescription water and sodium carboxymethylcellulose are joined in the mixer grinder, dissolving obtains aqueous high molecular solution fully under vacuum state; By prescription conductive black is added and dissolved in the good aqueous high molecular solution, agitation grinding to fineness is below the 5 μ m fast; Add Delanium by prescription again, vacuum stirs at a slow speed; Add the butylbenzene binding agent at last, vacuum stirs at a slow speed; Namely make required cathode size with 150 order stainless steel sift net filtrations.Cathode size is coated in the Copper Foil two sides that thickness is 8 μ m equably, again with roll squeezer with the pole piece compacting, last cut-parts, soldering polar ear namely obtain the water-base cathode sheet.
The preparation of positive plate: anode sizing agent is pressed the siccative weight percent meter, and its solid constituent comprises 90% positive active material, 5% PVDF(Kynoar) bonding agent and 5% conductive black, wherein, positive active material adopts cobalt acid lithium (LiCoO
2); It uses N-methyl pyrrolidone (NMP) as solvent, and the solids content of slurry is 40%.At first, by above prescription N-methyl pyrrolidone (NMP) and PVDF are joined in the mixer grinder, dissolving obtains PVDF solution fully under vacuum state; By prescription conductive black is joined and dissolve in the good oiliness PVDF solution, agitation grinding to fineness is below the 5 μ m fast; Add cobalt acid lithium by prescription at last, vacuum stirring is even; Namely make required anode sizing agent with 200 order stainless steel sift net filtrations.Anode sizing agent is coated in the aluminium foil two sides that thickness is 12 μ m equably, again with roll squeezer with the pole piece compacting, last cut-parts, soldering polar ear namely obtain the oiliness positive plate.
The preparation of electrolyte: ethylene carbonate EC, propene carbonate PC and dimethyl carbonate DMC are mixed with mixed solvent according to volume ratio 3:3:4, and then add solute lithium hexafluoro phosphate (LiPF
6), and make LiPF
6Concentration be 1M, obtain electrolyte after stirring.
The preparation of low melting point coating: with fusing point be 130 ℃ Witcodur 272 150 ℃ of fusings down, take advantage of heat rapidly on plus plate current-collecting body the position coating thickness of corresponding volume in-core portion be the coating of 30 μ m.
The preparation of barrier film: select for use thickness be polypropylene (PP) perforated membrane of 14 μ m as barrier film, and in the perforate of the position of corresponding low melting point coating, the size of perforate is half of low melting point coating spreading area, the position is in the central authorities of low melting point coating correspondence position.
The preparation of conductive resistance layer: the coating sizing-agent of conductive resistance layer is made up of 45% butylbenzene binding agent, 45% sodium carboxymethylcellulose, 10% conductive black, three parts.At first, by above prescription water and sodium carboxymethylcellulose are joined in the mixer grinder, dissolving obtains aqueous high molecular solution fully under vacuum state; By prescription conductive black is added and dissolved in the good aqueous high molecular solution, agitation grinding to fineness is below the 1 μ m fast; Add the butylbenzene binding agent by prescription at last, vacuum stirs at a slow speed; With 150 order stainless steel sift net filtrations, namely make required conductive resistance layer coating sizing-agent.Slurry is coated on the negative current collector, and the position is corresponding with the position of the last low melting point coating of plus plate current-collecting body.
The preparation of lithium ion battery: the positive plate, barrier film and the negative plate coiling that make are formed electric core, again with the aluminum plastic film encapsulation, and inject electrolyte; The encapsulation back changes into and burn-in test battery, obtains the square flexible packing lithium ion battery of length and width, the thick 32mm of being respectively, 82mm, 4.2mm.
Be with the difference of embodiment 1: conductive resistance layer coating sizing-agent is made up of 40% butylbenzene binding agent, 40% sodium carboxymethylcellulose and 20% conductive black, three parts.All the other materials are all identical with embodiment 1 with step etc., repeat no more herein.
Be with the difference of embodiment 1: conductive resistance layer coating sizing-agent is made up of 47.5% butylbenzene binding agent, 47.5% sodium carboxymethylcellulose and 5% conductive black, three parts.All the other materials are all identical with embodiment 1 with step etc., repeat no more herein.
Embodiment 4
Be with the difference of embodiment 1: positive plate uses 70% cobalt acid lithium (LiCoO
2) and 30% ternary material (LiNi
0.5Co
0.2Mn
0.3) mix as positive active material, two kinds of materials proportion in the anode sizing agent solid constituent still is 90%.All the other materials are all identical with embodiment 1 with step etc., repeat no more herein.
Difference from Example 1 is: the preparation process of low melting point coating is, with fusing point be 110 ℃ Tissuemat E 150 ℃ of fusings down, take advantage of heat rapidly on plus plate current-collecting body the position coating thickness of corresponding volume in-core portion be the coating of 30 μ m.All the other materials are all identical with embodiment 1 with step etc., repeat no more herein.
Embodiment 6
Difference from Example 1 is:
The preparation of low melting point coating: with fusing point be 130 ℃ polypropylene 150 ℃ of fusings down, take advantage of heat rapidly on negative current collector the position coating thickness of corresponding volume in-core portion be the coating of 30 μ m;
The preparation of barrier film: select for use thickness be polypropylene (PP) perforated membrane of 14 μ m as barrier film, and in the perforate of the position of corresponding low melting point coating, the size in hole is half of low melting point coating spreading area, the position is in the central authorities of low melting point coating correspondence position;
The preparation of conductive resistance layer: the coating sizing-agent of conductive resistance layer is made up of 45% butylbenzene binding agent, 45% sodium carboxymethylcellulose, 10% conductive black, three parts.At first, by above prescription water and sodium carboxymethylcellulose are joined in the mixer grinder, dissolving obtains aqueous high molecular solution fully under vacuum state; By prescription conductive black is added and dissolved in the good aqueous high molecular solution, agitation grinding to fineness is below the 1 μ m fast; Add the butylbenzene binding agent by prescription at last, vacuum stirs at a slow speed; With 150 order stainless steel sift net filtrations, namely make required conductive resistance layer coating sizing-agent.Slurry is coated on the plus plate current-collecting body, and the position of low melting point coating is corresponding on position and the negative current collector.
All the other materials are all identical with embodiment 1 with step etc., repeat no more herein.
Comparative Examples 1
Be with the difference of embodiment 1: be not coated with the low melting point coating on the plus plate current-collecting body, not perforate on the barrier film is not coated with the conductive resistance layer on the negative current collector.All the other materials are all identical with embodiment 1 with step etc., repeat no more herein.
Comparative Examples 2
Be with the difference of embodiment 1: be not coated with the conductive resistance layer on the negative current collector.All the other materials are all identical with embodiment 1 with step etc., repeat no more herein.
Overcharge test
At room temperature, with the 1C multiplying power battery of Comparative Examples 1, Comparative Examples 2 and embodiment 1 is carried out constant current charge, be charged to constant voltage charge behind the 6V, obtain Fig. 4, Fig. 5 and the curve that overcharges shown in Figure 6 respectively.As shown in Figure 4, the normal battery of Comparative Examples 1 temperature in lasting high-voltage charge process rises gradually, and when temperature reached 110 ℃ of left and right sides, temperature rose rapidly and final burning.As shown in Figure 5, Comparative Examples 2 is coated with the battery of low melting point coating when temperature reaches 90 ℃ of left and right sides, internal short-circuit of battery, and charging voltage reduces rapidly; But after the short circuit, because interior resistance is very little, produces very imperial palace electric current and a large amount of heat release, thereby accelerate the battery burning.As shown in Figure 6, the battery of embodiment 1, when the constant-voltage phase temperature arrives 100 ℃ of left and right sides, internal short-circuit of battery, temperature namely begins to descend, and finally makes cell safety by overcharging test.As seen, lithium ion battery of the present invention can guarantee safety under the state of overcharging.
In sum, the present invention is by the coating of the subregion on negative current collector or plus plate current-collecting body one deck low melting point coating, correspondence position coating one deck conductive resistance layer at another collector, and offer perforate at the correspondence position of barrier film, thereby make battery after the state of overcharging is issued to uniform temperature, the low melting point coating melts and forms the both positive and negative polarity short dot at the barrier film tapping, thereby reaches the effect of shunting, reduces the electric current by pole piece; Simultaneously, the conductive resistance layer of coating can reduce the electric current that internal short-circuit produces, and reduces heat release, finally reaches the function of over-charge protective, avoids battery blast on fire, and increases the fail safe of battery.
Compared with prior art, lithium ion battery of the present invention has the following advantages at least:
The first, have good over-charge protective performance, can guarantee cell safety high-tension the overcharging under the state of high electric current, and can under the state that overcharges that continues, guarantee cell safety;
The second, because the over-charge protective method that adopts is physical method, therefore can not produce big influence to the chemical property of battery, can guarantee the performance of battery.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also carry out suitable change and modification to above-mentioned execution mode.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition, although used some specific terms in this specification, these terms do not constitute any restriction to the present invention just for convenience of description.
Claims (10)
1. lithium ion battery, comprise positive plate, negative plate and be interval in barrier film between the positive/negative plate, positive plate comprises plus plate current-collecting body and the anodal diaphragm of coating on the plus plate current-collecting body, negative plate comprises negative current collector and the cathode membrane of coating on the negative current collector, it is characterized in that: the subregion on described plus plate current-collecting body or the negative current collector is coated with one deck low melting point coating, the position corresponding with the low melting point coating is coated with one deck conductive resistance layer on another collector, barrier film with the low melting point coating, the corresponding position of conductive resistance layer offers perforate and the low melting point coating directly contacted with the conductive resistance layer.
2. lithium ion battery according to claim 1, it is characterized in that: the fusing point of described low melting point coating is between 60 ℃ to 200 ℃.
3. lithium ion battery according to claim 1 is characterized in that: the thickness of described low melting point coating at 5 μ m between the 200 μ m.
4. lithium ion battery according to claim 1, it is characterized in that: described low melting point coating is the coating that is insoluble to electrolyte, its swellbility in electrolyte is less than 100%.
5. lithium ion battery according to claim 1, it is characterized in that: described low melting point coating is a kind of or its combination in paraffin, Witcodur 272, Ployethylene Wax, the polypropylene.
6. lithium ion battery according to claim 1 is characterized in that: the resistivity of described conductive resistance layer at 0.5 Ω/m between 200 Ω/m.
7. lithium ion battery according to claim 1 is characterized in that: the thickness of described conductive resistance layer at 5 μ m between the 200 μ m.
8. lithium ion battery according to claim 1 is characterized in that: the perforate size of described barrier film account for place, plane, perforate place on the volume core cross-sectional area 5%～100%.
9. lithium ion battery according to claim 1 is characterized in that: described conductive resistance layer forms by the slurry coating that contains butylbenzene binding agent, sodium carboxymethylcellulose and conductive black.
10. according to each described lithium ion battery in the claim 1 to 9, it is characterized in that: described lithium ion battery is the winding type lithium ion battery, and low melting point coating and conductive resistance layer are coated on the coiling initiating terminal of positive/negative plate or finish end.
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|---|---|---|---|
| CN201310213734.3A CN103280597B (en) | 2013-05-31 | 2013-05-31 | Lithium ion battery |
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| CN105449263A (en) * | 2014-08-22 | 2016-03-30 | 宁德时代新能源科技股份有限公司 | Lithium ion secondary battery |
| CN105974319A (en) * | 2016-04-21 | 2016-09-28 | 中国民航大学 | 18650 lithium battery thermal runaway chain reaction test method |
| CN107645001A (en) * | 2017-08-21 | 2018-01-30 | 上海空间电源研究所 | A kind of experimental rig and test method for simulating lithium battery internal short-circuit |
| CN110265665A (en) * | 2019-05-24 | 2019-09-20 | 宁德时代新能源科技股份有限公司 | Positive current collector, positive pole piece and electrochemical device |
| CN110824372A (en) * | 2019-11-25 | 2020-02-21 | Oppo广东移动通信有限公司 | Method and equipment for judging short circuit in battery and electronic equipment |
| CN113826277A (en) * | 2020-03-27 | 2021-12-21 | 宁德新能源科技有限公司 | Electrochemical device and electronic device comprising same |
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| CN113826277A (en) * | 2020-03-27 | 2021-12-21 | 宁德新能源科技有限公司 | Electrochemical device and electronic device comprising same |
| CN113826277B (en) * | 2020-03-27 | 2023-09-01 | 宁德新能源科技有限公司 | Electrochemical device and electronic device comprising same |
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|---|---|
| CN103280597B (en) | 2017-09-29 |
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