CN105826512A - Method for increasing cycle life of lithium ion battery based on thermal conductivity - Google Patents
Method for increasing cycle life of lithium ion battery based on thermal conductivity Download PDFInfo
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- CN105826512A CN105826512A CN201510009140.XA CN201510009140A CN105826512A CN 105826512 A CN105826512 A CN 105826512A CN 201510009140 A CN201510009140 A CN 201510009140A CN 105826512 A CN105826512 A CN 105826512A
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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 a method for increasing cycle life of a lithium ion battery by increasing thermal conductivity of an electrode of the lithium ion battery. The method comprises the following steps: a heat conduction material having superhigh electric conduction and thermal conductivity is added in a positive pole piece of the lithium ion battery, and the flexibly packaged lithium ion battery is made. The heat conduction material is graphene or a carbon fiber material; the carbon fiber material comprises a hollow carbon nanotube and solid carbon nano fiber. The graphene and the carbon fiber material have excellent thermal conductivity, thereby, addition of graphene and the carbon fiber material can rapidly, uniformly and fully transmit heat generated during a charge and discharge process of the battery, uneven temperature in the batter due to accumulation of local heat is reduced, therefore, area degradation of the lithium ion battery is improved, the charge and discharge cycle efficiency of the battery is improved, and cycle life and security are increased.
Description
Technical field
The present invention relates to technical field of lithium ion, it particularly relates to improve the process of cycle life of lithium ion battery by improving battery heat conductivity.
Background technology
Lithium ion battery is high due to running voltage; volume is little, light weight, and energy is high; memory-less effect; pollution-free, self discharge is little, especially peters out and today to environmental protection problem pay attention to day by day at traditional fossil energy; lithium ion battery is as the preferable efficient green energy; receive attention especially, obtain each automobile vendor and the accreditation of battery production manufacturer, be considered the preferable energy of 21 century development.
Although lithium ion battery has certain advantage in terms of replacement traditional storage battery is as electrical source of power such as electric motor car, hybrid electric vehicle, electric bicycle and electric tools, but lithium ion battery is at work, along with the number of times of discharge and recharge increases and the aging of battery, internal resistance can increase, these heats that battery all can be caused in use self to produce increase, and the heat that in battery, various processes produce includes polarizing thermally and chemically reaction heat.Polarization heat depends mainly on the internal resistance of cell, including electrode and electrolyte interface, barrier film, electrolyte, collector and the resistance of metal tabs, chemical reaction heat refers to form the chemical reaction between substances heat of battery, it is probably exothermic reaction, being also likely to be the endothermic reaction, whether these strong reactions change with temperature difference.
After lithium ion battery maximizes, capacity is high, size is big, heat radiation is the weakest for comparing heat production, if the heat that battery produces in the course of the work can not conduct at inside battery in time uniformly, battery temperature can be caused uneven, as a example by lithium ion soft-package battery, in inside lithium ion cell anode pole piece, if the poor thermal conductivity of battery, battery pole piece temperature is uneven, it is overheated that amount of localized heat accumulation causes, the pole piece chemical property that can make this region lost efficacy and accelerated, cause by the CURRENT DISTRIBUTION of pole piece uneven, and then make the polarization between whole pole piece zones of different become big, have a strong impact on the service life that battery is overall.
In recent years, there is super good conduction and the grapheme material of heat conductivity and carbon fibre material (including carbon nanotubes and solid carbon nanofiber) paid high attention to by more and more Study on Li-ion batteries personnel, one research of California, USA university shows, the heat conductivility of the material such as Graphene and CNT is superior, especially Graphene, it is referred to as the material with best heat conductivity, their heat conductivity is significantly larger than the metal material of other material with carbon elements and high-termal conductivity, such as silver, copper, gold, aluminum etc..The heat conductivity of common CNT is up to more than 3000W/mK, and the heat conductivity of single-layer graphene, up to 5300W/mK, even there are some researches show that its heat conductivity is up to 6600W/mK.It addition, grapheme material and carbon fibre material join in the middle of positive electrode, additionally it is possible to build perfect conductive network as conductive agent, improve the electric conductivity of pole piece, reduce ohmic polarization heat.The heat that battery produces in the course of the work more can be transmitted rapidly and uniformly by the heat conductivility of its excellence in inside, reduce and bring because of the accumulation of amount of localized heat internal temperature of battery uneven, thus, the region deterioration of lithium ion battery can be improved, and improve the charge and discharge cycles efficiency of battery the most further, improve cycle life and safety thereof.
Summary of the invention
In order to improve lithium ion cycle life in charge and discharge process, in the present invention, it is proposed that based on improving lithium ion battery heat conductivity and then reducing cell area deterioration, and improve the research method of cycle life.
The present invention disclose a kind of by improve lithium ion battery heat conductivity thus thus improve the experimental technique of cycle life of lithium ion battery.The method mainly includes, adds the Heat Conduction Material additive with super good conduction and heat conductivity in anode slice of lithium ion battery preparation process；Wherein, described Heat Conduction Material is grapheme material and carbon fibre material (including carbon nanotubes and solid carbon nanofiber)；After additives different in above-mentioned Heat Conduction Material is carried out independent or combination of two or three's combination, according to a certain percentage, add to and positive active material is prepared positive plate, and make soft bag lithium ionic cell.
The step of the concrete preparation method of its battery anode slice is as follows:
1, first weigh a certain amount of positive electrode, then weigh conductive agent and the binding agent of certain mass according to the amount of positive electrode；
2, Heat Conduction Material has been weighed standby also according to corresponding ratio and category combinations；
3, each component material weighed up is put in vacuum drying oven carries out the drying of more than 12h；
4, binding agent is joined in solvent NMP (N-methyl ketopyrrolidine) and carry out gluing；
5, successively conductive agent, Heat Conduction Material and positive electrode are added separately in the glue accomplished fluently, are enclosed in blender and are stirred until forming uniform slurry；
6, mixed slurry is coated, cutting and baking, standby.
Wherein, positive electrode is preferential, for spinelle LMn2O4, stratiform Li [NixCoyMnz]O2(wherein 0≤x < 1,0≤y < 1,0≤z < 1) and stratiform richness lithium material aLi2MnO3-bLi[NixCoyMnz]O2(wherein, a+b=1,0≤x < 1,0≤y < 1,0≤z < 1).
Wherein, used conductive agent is preferential, for one or more the combination such as electrically conductive graphite, activated carbon, amorphous carbon or conductive black.
Wherein, used binding agent is preferential, for various series binding agent (e.g., polytetrafluoroethylene PTFE) that Kynoar (PVDF) is main component.
Wherein, Heat Conduction Material, preferential, for Graphene, CNT and carbon nano-fiber therein any one, two or three combination, its quality proportion in raw material (in addition to the solvents) gross mass of whole positive plate is 0.01～10%.
Wherein, preferential, the quality proportioning of active substances in cathode materials is 80-99%, and conductive agent is 0.1～19%, and binding agent is 0.5～10%.
Anode pole piece made in the present invention, can apply to flexible packing lithium ion in the battery, and it has the following advantages that and effect:
In the present invention, by adding high connductivity and Heat Conduction Material Graphene, CNT and carbon Nanowire, they are added directly in positive electrode with independent or combination form and directly participate in slurry, do not result in the increase of process and complexity, simple easily realization.And, the Heat Conduction Material additive added, the capacity of heat transmission of lithium ion battery can not only be improved, reduce and bring because of the accumulation of amount of localized heat internal temperature of battery uneven, improve the region deterioration of lithium ion battery, improve the life-span, meanwhile, this additive also has extremely strong electric conductivity, it is possible to build perfect conductive network as conductive agent, improve the electric conductivity of pole piece, and then improve the combination property of lithium ion battery.
Accompanying drawing explanation
For technical scheme involved in the clearer explanation present invention and the improvement of correlated performance that thus brings thereof; the accompanying drawing used required in the embodiment of the present invention will be introduced simply below; for in this technical field; under the premise without departing from the principles of the invention; its figure is likely to be modified or modify, but these figures are also intended to implement within the scope of the invention as claimed.
Fig. 1 is anode pole piece local wide electron microscope picture in the embodiment of the present invention 1；
Fig. 2 is in the embodiment of the present invention, is not added with in thermal conducting agent and embodiment 2 adding the electronic conductivity cylindricality comparison diagram of thermal conducting agent Graphene positive plate in comparative example；
Fig. 3 is the thermal imaging comparison diagram of lithium ion battery obtained by pole piece in embodiment 2 in the present invention, and Fig. 3-1 is the comparative example not adding thermal conducting agent, and Fig. 3-2 is the embodiment 2 adding thermal conducting agent.
Fig. 4 is lithium ion battery obtained by pole piece and the discharge capacity cycle performance figure under comparative example 55 DEG C of 1C of common pole piece lithium ion battery in the embodiment of the present invention 3.
Detailed description of the invention
Embodiment 1
1) LiMn2O4 LiMn is weighed2O4915g, PVDF45g, conductive black SP and electrically conductive graphite KS15 20g, CNT (CNTS) 20g altogether, be placed on the material weighed in 100 DEG C of high-temperature vacuum baking ovens and carry out toasting a whole night, standby.
2) PVDF is joined in solvent NMP (N-methyl ketopyrrolidine) and carry out gluing.
3) by 1) in each material and 2 of drying) in the glue accomplished fluently join in planetary de-airing mixer, carry out evacuation stirring 3～5h, form uniform slurry.
4) slurry of mix homogeneously is sieved, and measure particle sice in serosity and viscosity.
5) slurry is carried out on coating machine positive and negative coating.
6) coated pole piece is carried out cutting trimming, place vacuum drying oven and toast.
7) pole piece being baked is carried out roll-in, then according to the design size of lithium ion battery flexible package carries out final cutting.
8) anode pole piece cut out is taken sample carry out SEM sweep test see Fig. 1 and electronic conductivity test.
9) anode pole piece cut out is assembled with corresponding negative pole, barrier film and lug etc., make complete lithium ion battery.
10) in order to prove the raising of heat conductivity, complete battery has been carried out thermal imaging test, meanwhile, has been also carried out the test of electrochemistry high temperature cyclic performance, in order to prove the raising adding this Heat Conduction Material to cycle life.
As shown in Figure 1, add CNT can be highly uniform be coated on spinel lithium manganate particle surface, define the macroreticular of a distribution dense uniform, so, so that each point can react uniformly in battery charge and discharge process on positive active material granule, reduce the polarization phenomena of battery.
Embodiment 2
1) LiMn2O4 LiMn is weighed2O4915g, PVDF45g, conductive black SP and electrically conductive graphite KS15 20g, Graphene 20g altogether, be placed on the material weighed in 100 DEG C of high-temperature vacuum baking ovens and carry out toasting a whole night, standby.
2～7) with embodiment 1.
8) anode pole piece cut out is taken sample carry out SEM sweep test and electronic conductivity test see Fig. 2.
9) with embodiment 1.
10) in order to prove the raising of heat conductivity, complete battery is carried out thermal imaging test, has seen Fig. 3, meanwhile, be also carried out the test of electrochemistry high temperature cyclic performance, in order to prove the raising adding this Heat Conduction Material to cycle life.
As shown in Figure 2, after with the addition of Graphene, with un-added electric conductivity is greatly improved compared with the common anode pole piece of proportioning, thus can reduce lithium ion battery ohm heat in charge and discharge process, also can improve the chemical property of battery simultaneously.
As shown in Figure 3, battery is carried out thermal imaging test, from thermograph this it appears that, the temperature spread of its pole piece different parts of battery that with the addition of Graphene Heat Conduction Material is little, entirety is more average, and this illustrates that this material serves good cell heat transfer conductive force, it is possible to reduce the polarization phenomena that battery causes because of the difference of local response speed, and not adding the common lithium manganate battery of heat conduction additive, the temperature difference of its same pole piece diverse location is bigger.
Embodiment 3
1) LiMn2O4 LiMn is weighed2O4915g, PVDF45g, conductive black SP and electrically conductive graphite KS15 20g, Graphene 10g, CNT (CNTS) 10g altogether, be placed on the material weighed in 100 DEG C of high-temperature vacuum baking ovens and carry out toasting a whole night, standby.
2～9) with embodiment 1.
10) in order to prove the raising of heat conductivity, complete battery has been carried out thermal imaging test, meanwhile, has been also carried out the test of electrochemistry high temperature cyclic performance, sees Fig. 4, in order to prove the raising adding this Heat Conduction Material to cycle life.
As shown in Figure 4, lithium manganate battery carrying out under the multiplying power of 55 DEG C of 1C charge and discharge cycles test, the battery cycle life that with the addition of thermal conducting agent combination (Graphene and CNTS) is significantly better than un-added common lithium manganate battery.
Embodiment 4
1) LiMn2O4 LiMn is weighed2O4800g, PVDF100g, conductive black SP and electrically conductive graphite KS15 80g, Graphene 10g, CNT (CNTS) 5g, carbon nano-fiber 5g altogether, be placed on the material weighed in 100 DEG C of high-temperature vacuum baking ovens and carry out toasting a whole night, standby.
2～10) with embodiment 1.
Embodiment 5
1) LiMn2O4 LiMn is weighed2O4950g, PVDF15g, conductive black SP and electrically conductive graphite KS15 20g, carbon nano-fiber 15g altogether, be placed on the material weighed in 100 DEG C of high-temperature vacuum baking ovens and carry out toasting a whole night, standby.
2～10) with embodiment 1.
Embodiment 6
1) ternary material Li [Ni is weighed1/3Co1/3Mn1/3]O2915g, PVDF45g, conductive black SP and electrically conductive graphite KS15 5g, Graphene 35g altogether, be placed on the material weighed in 100 DEG C of high-temperature vacuum baking ovens and carry out toasting a whole night, standby.
2～10) with embodiment 1.
Embodiment 7
1) ternary material Li [Ni is weighed1/3Co1/3Mn1/3]O2950g, PVDF15g, conductive black SP and electrically conductive graphite KS15 5g, CNT (CNTS) 30g altogether, be placed on the material weighed in 100 DEG C of high-temperature vacuum baking ovens and carry out toasting a whole night, standby.
2～10) with embodiment 1.
Embodiment 8
1) ternary material Li [Ni is weighed1/3Co1/3Mn1/3]O2850g, PVDF25g, conductive black SP and electrically conductive graphite KS15 25g, Graphene 50g, CNT (CNTS) 50g altogether, be placed on the material weighed in 100 DEG C of high-temperature vacuum baking ovens and carry out toasting a whole night, standby.
2～10) with embodiment 1.
Embodiment 9
1) ternary material Li [Ni is weighed1/3Co1/3Mn1/3]O2900g, PVDF45g, conductive black SP and electrically conductive graphite KS15 20g, carbon nano-fiber 25g altogether, be placed on the material weighed in 100 DEG C of high-temperature vacuum baking ovens and carry out toasting a whole night, standby.
2～10) with embodiment 1.
Embodiment 10
1) ternary material Li [Ni is weighed1/3Co1/3Mn1/3]O2900g, PVDF15g, conductive black SP and electrically conductive graphite KS15 30g, Graphene 20g, CNT (CNTS) 15g, carbon nano-fiber 20g altogether, be placed on the material weighed in 100 DEG C of high-temperature vacuum baking ovens and carry out toasting a whole night, standby.
2～10) with embodiment 1.
Embodiment 11
1) lithium-rich material 0.3Li is weighed2MnO3-0.7Li[Ni0.5Mn0.5]O2910g, PVDF25g, conductive black SP and electrically conductive graphite KS15 20g, Graphene 45g altogether, be placed on the material weighed in 100 DEG C of high-temperature vacuum baking ovens and carry out toasting a whole night, standby.
2～10) with embodiment 1.
Embodiment 12
1) lithium-rich material 0.3Li is weighed2MnO3-0.7Li[Ni0.5Mn0.5]O2870g, PVDF45g, conductive black SP and electrically conductive graphite KS15 20g, CNT (CNTS) 65g altogether, the material weighed is placed in 100 DEG C of high-temperature vacuum baking ovens and carries out toasting a whole night, standby.
2～10) with embodiment 1.
Embodiment 13
1) lithium-rich material 0.3Li is weighed2MnO3-0.7Li[Ni0.5Mn0.5]O2960g, PVDF15g, conductive black SP and electrically conductive graphite KS15 10g, Graphene 5g, CNT (CNTS) 5g, carbon nano-fiber 5g altogether, be placed on the material weighed in 100 DEG C of high-temperature vacuum baking ovens and carry out toasting a whole night, standby.
2～10) with embodiment 1.
Embodiment 14
1) lithium-rich material 0.3Li is weighed2MnO3-0.7Li[Ni0.5Mn0.5]O2905g, PVDF15g, conductive black SP and electrically conductive graphite KS15 40g, carbon nano-fiber 40g altogether, be placed on the material weighed in 100 DEG C of high-temperature vacuum baking ovens and carry out toasting a whole night, standby.
2～10) with embodiment 1.
Embodiment 15
1) lithium-rich material 0.3Li is weighed2MnO3-0.7Li[Ni0.5Mn0.5]O2910g, PVDF20g, conductive black SP and electrically conductive graphite KS15 30g, Graphene 15g, CNT (CNTS) 25g altogether, be placed on the material weighed in 100 DEG C of high-temperature vacuum baking ovens and carry out toasting a whole night, standby.
2～10) with embodiment 1.
Comparative example
1) LiMn2O4 LiMn is weighed2O4915g, PVDF45g, conductive black SP and electrically conductive graphite KS15 20g altogether, is placed on the material weighed in 100 DEG C of high-temperature vacuum baking ovens and carries out toasting a whole night, standby.
2～10) with embodiment 1.
Above; thered is provided the inventive method several is described in detail; wherein; in description, specific embodiment is in order to more preferable principle and embodiment for inventive method is illustrated; for in this technical field; other data all under the premise without departing from the principles of the invention and to its amendment and modification, are also intended to implement within the scope of the invention as claimed.
Claims (9)
1. the method improving cycle life of lithium ion battery based on heat conductivity, it is characterized in that, the method is: when preparing positive plate, adds in the mixing raw material of preparing positive plate as additive according to certain ratio using Heat Conduction Material, to prepare the positive plate of high heat conduction.
Method the most according to claim 1, it is characterised in that described Heat Conduction Material is Graphene, carbon fibre material or its mixture；Wherein, carbon fibre material includes hollow CNT and solid carbon nano-fiber.
3. according to the method described in claim 1 or 2, it is characterised in that the quality of described Heat Conduction Material is the 0.01-10% of positive pole raw material gross mass in addition to the solvents.
Method the most according to claim 3, it is characterized in that, prepare each raw material needed for positive plate and account for the mass percent of raw material gross mass and be: positive active material 80-99%, conductive agent 0.1～19%, Heat Conduction Material 0.01～10% and binding agent 0.5～10%.
5. according to the method described in claim 4, it is characterised in that described positive active material specifically includes that spinelle LMn2O4, stratiform Li [NixCoyMnz]O2(wherein 0≤x < 1,0≤y≤1,0≤z < 1) and stratiform richness lithium material aLi2MnO3-bLi[NixCoyMnz]O2(wherein, a+b=1,0≤x < 1,0≤y < 1,0≤z < 1) and their combination in any.
6. according to the method described in claim 4, it is characterised in that described conductive agent is the combination of one or more in electrically conductive graphite, activated carbon, amorphous carbon or conductive black.
7. according to the method described in claim 4, it is characterised in that described binding agent is Kynoar or politef.
8. according to the method described in right 3 requirement, it is characterised in that described Heat Conduction Material is any one or a few combination mixed with arbitrary proportion in Graphene, CNT and carbon nano-fiber.
9. the based lithium-ion battery positive plate of high heat conduction prepared according to the method described in any of the above-described claim and the lithium ion battery being made up of this positive plate again.
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| CN107204452A (en) * | 2017-05-25 | 2017-09-26 | 东南大学 | A kind of graphene anode material for improving lithium ion battery overcharge safety |
| CN107271904A (en) * | 2017-05-24 | 2017-10-20 | 苏州宇量电池有限公司 | Measuring device for heat yield during circulating battery |
| WO2018177175A1 (en) * | 2017-03-25 | 2018-10-04 | 华为技术有限公司 | Battery electrode, preparation method thereof and battery |
| CN109596986A (en) * | 2018-12-29 | 2019-04-09 | 蜂巢能源科技有限公司 | Power battery pack internal resistance estimation on line method and battery management system |
| CN112151742A (en) * | 2020-09-25 | 2020-12-29 | 福建师范大学 | Preparation method of ternary cathode material modified by metal oxide and graphene and used for improving performance of full battery |
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Application publication date: 20160803 |