CN105514521A - Lithium ion battery with temperature regulation function - Google Patents
Lithium ion battery with temperature regulation function Download PDFInfo
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- CN105514521A CN105514521A CN201510890561.8A CN201510890561A CN105514521A CN 105514521 A CN105514521 A CN 105514521A CN 201510890561 A CN201510890561 A CN 201510890561A CN 105514521 A CN105514521 A CN 105514521A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
- 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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Abstract
The invention relates to the technical field of batteries, in particular to a lithium ion battery with a temperature regulation function. The lithium ion battery comprises a positive pole, a negative pole, a cell, an electrolyte of the cell and a solid-solid phase change material, wherein the cell is formed by winding a diaphragm arranged between the positive pole and the negative pole in a spaced manner; the solid-solid phase change material is added to at least one of the positive pole, the negative pole, the cell and the electrolyte. Compared with the prior art, the solid-solid phase change material is added to inner side or outer side of the lithium ion battery, so that the high-and-low temperature performance of the lithium ion battery is improved effectively on the premise that the performance of the battery is not affected.
Description
Technical field
The present invention relates to cell art, particularly relate to a kind of lithium ion battery possessing temp regulating function.
Background technology
Lithium ion battery because have energy density high, have extended cycle life, the feature such as the more excellent and environmental friendliness of mechanical performance, be widely used on the energy storage devices such as various consumption electronic product, various electric automobile and wind and solar energy.For lithium ion battery, no matter be cell or cell is assembled into battery pack, the various problems caused because temperature is too high or temperature is too low in use all can be there are.Reason is lithium ion battery is a kind of battery very responsive to temperature, and under normal circumstances, during lithium-ion electric tank discharge, temperature range is at-20 ~+60 DEG C; During charging, temperature range is at 0 ~+45 DEG C.At low temperatures to lithium ion cell charging, easily cause the generation of Li dendrite, cause the generation of battery internal short-circuit, thus bring out safety problem; And at high temperature discharge and recharge is carried out to lithium ion battery, easily bring out side reaction in battery, cause the generation of degradation bad phenomenon under battery capacity decay, internal resistance increase, cycle life.
In the prior art, general by adding protection additive in the electrolyte of battery, to improve the performance under battery low temperature and high temperature.But because the chemical characteristic by additive limits, the cryogenic property of battery can be reduced when promoting battery high-temperature behavior, the high-temperature behavior of battery can be destroyed when promoting battery cryogenic property, the working temperature window of battery cannot be made effectively to be expanded.
In recent years, developing rapidly of phase-changing energy storage material, provides new approaches for improving battery high temperature performance, and phase-change material is that a kind of physical property that changes along with variations in temperature also realizes the absorption of heat or the material of release.Utilize the phase transformation reaction that phase-change material occurs under different temperatures environment, carry out heat supplement or carry out heat to battery drawing to battery, thus reach at low temperatures to battery surface intensification, at high temperature to the effect of battery surface cooling.
If number of patent application is the Chinese patent of 201110242038.6, disclose the battery pack that one has phase-change material (PCM), the spacer be arranged between battery unit includes phase-change material, but because this phase-change material is arranged at outside batteries, its temperature control effect is poor compared to being arranged on inside battery; And its selection is solid-liquid phase change material, and easily reveals during solid-liquid phase change and corrode, therefore solid-liquid phase change material can not add cell inside to, otherwise easily produce safety problem.
Summary of the invention
The object of the invention is to: a kind of lithium ion battery possessing temp regulating function is provided for the deficiencies in the prior art, by adding solid-solid phase change material in the inside of lithium ion battery or outside, under the prerequisite not affecting battery self performance, the high temperature performance of lithium ion battery is effectively improved.
To achieve these goals, the invention provides following solution:
A kind of lithium ion battery possessing temp regulating function, comprise positive pole, negative pole and to be interposed between the battery core of the membrane winding between described positive pole and described negative pole, and electrolyte, also comprise solid-solid phase change material, described solid-solid phase change material is added at least one place of described positive pole, described negative pole, described barrier film, described electrolyte.
General phase-change material is divided into solid-solid phase change material, solid-liquid phase change material and solid-gas reaction material.The present invention utilizes phase-change material self character, and when battery temperature reaches the phase transition temperature of phase-change material, phase-change material phase in version process can occur and carries out absorbing heat or heat release.That is, when internal temperature of battery is lower than phase transition temperature, phase change material releases heat; When internal temperature of battery is higher than phase transition temperature, phase-change material absorbs heat.And the phase-change material that the present invention chooses is solid-solid phase change material, compared with solid-liquid phase change material or solid-gas reaction material, what solid-solid phase change material occurred is the transformation of solid phase, in phase transition process, no liquid or gas produce or absorb, any destruction can not be brought to battery performance, also can not bring out the side reaction of inside battery, under the prerequisite ensureing battery safety and reliability, expand the operating temperature range of battery.
Wherein, described positive pole comprises plus plate current-collecting body and positive pole diaphragm thereof, and described negative pole comprises negative current collector and cathode membrane thereof.In cell fabrication processes, solid-solid phase change material can be coated between both positive and negative polarity collector and both positive and negative polarity diaphragm, also can directly be added in the raw material of both positive and negative polarity diaphragm.When both positive and negative polarity surface temperature is lower than phase transition temperature, solid-solid phase change material, to both positive and negative polarity heat release, improves both positive and negative polarity surface temperature; When both positive and negative polarity surface temperature is higher than phase transition temperature, solid-solid phase change material absorbs heat to both positive and negative polarity, reduces both positive and negative polarity surface temperature.
General battery diaphragm is macromolecular compound, and therefore, the solid-solid phase change material Ying Yuqi being added on battery diaphragm has good compatibility, such as can choose crosslinked high density polyethylene (HDPE).Phase in version process under high temperature absorbs the heat that inside battery produces, and gives the hot shock-absorbing capacity of barrier film excellence, and the barrier film fusing avoiding internal temperature of battery to rise sharply causing and cell damage, substantially increase the fail safe of battery, extend the useful life of battery.
Lithium ion battery electrolyte used is generally organic liquid, as grease, can become sticky at low temperatures and thickly even to condense.Now, the lithium salts activity inside of conduction is restricted greatly, causes charge efficiency very low, thus occurs that battery charges slowly at low temperatures, the phenomenon be not fully filled.And after adding solid-solid phase change material in the electrolytic solution, the generation of this phenomenon can be avoided.
As a further improvement on the present invention, described solid-solid phase change material is covered on the outer surface of described battery core.Compared to the inside being added on battery, outer surface solid-solid phase change material being covered in battery core is not only easy and simple to handle, and can carry out Effective Regulation to the surface temperature of battery equally.
As a further improvement on the present invention, the phase transition temperature range of described solid-solid phase change material is-40 DEG C ~ 150 DEG C.Preferably, the phase transition temperature range of described solid-solid phase change material is-20 DEG C ~ 85 DEG C.Because lithium ion battery generally normally works in 0 DEG C ~ 60 DEG C temperature ranges, the charge-discharge performance exceeding this temperature range lithium ion battery can be affected.If temperature declines, the reactivity of battery plus-negative plate also declines, and supposes cell voltage holding constant, and discharging current reduces, and the power output of battery also can decline; If temperature rises, contrary, namely cell output can rise.If temperature is too high, such as reach 150 DEG C, the heat-seal characteristic of battery can be destroyed, cause battery thermal runaway; Generally, when temperature is more than 60 DEG C, then can destroy the chemical balance in battery, cause the generation of side reaction.If temperature is too low, such as lower than-40 DEG C, the protection components and parts sensitivity decrease of mating with battery, will lose the defencive function to battery; Generally, when temperature is lower than-20 DEG C, because electrolyte viscosity increases and the reduction of battery material liveness, the discharging efficiency of battery is caused to have significant reduction.Therefore, battery temperature is controlled-40 DEG C ~ 150 DEG C temperature ranges or narrower temperature range very important.
As a further improvement on the present invention, described solid-solid phase change material comprises at least one of organic solid-solid phase change material, inorganic solid-solid phase change material, composite solid solid phase change material.
As a further improvement on the present invention, described Solid Organic solid phase change material is at least one in crosslinked high density polyethylene (HDPE) (HDPE), crosslinked polyformaldehyde (POM), pentaerythrite (PE), neopentyl glycol (NPG), dihydroxymethyl ethane (PG), AMPD (AMP) and trishydroxymethylaminomethane (TAM).
As a further improvement on the present invention, described inorganic solid-solid phase change material is NH
4sCN, Li
2sO
4, KHF
2, at least one in Al-Si, Cu-Si.
As a further improvement on the present invention, described composite solid solid phase change material is (n-C
nh
2n-1nH
3)
2mX
1, wherein: X is chlorine, n is carbon number (n=8 ~ 18), and M is any one in Mn, Cu, Fe, Cd, Ni, Zn, Co.Composite phase-change material is organic and inorganic composite material, and it effectively can overcome the shortcoming that single inorganic or organic phase change material exists, and can improve again the effect of phase-change material and expand its range of application.
Beneficial effect of the present invention: by adding solid-solid phase change material in the inside of lithium ion battery or outside, under battery is in low-temperature condition, solid-solid phase change material heat release, carries out heat supplement to battery, makes battery operating temperature increase; Under battery is in the condition of high temperature, solid-solid phase change material absorbs heat, and carries out heat extraction, battery operating temperature is declined to battery.Under the prerequisite not affecting battery self performance, the high temperature performance of lithium ion battery is effectively improved.
Embodiment
Below in conjunction with specific embodiment, the present invention and beneficial effect thereof are described in further detail, but the specific embodiment of the present invention is not limited thereto.
Embodiment 1
The preparation of positive pole: by cobalt acid lithium (positive active material), conductive agent superconduction carbon (Super-P), bonding agent Kynoar (PVDF), solid-solid phase change material Al-Si in mass ratio 94:2.5:2.0:1.5 mix the lithium ion battery anode glue size made and there is certain viscosity, slurry is coated in current collector aluminum foil, colds pressing after drying at 80 DEG C; Then carry out trimming, cut-parts, itemize, after itemize under vacuum 80 DEG C dry 5 hours, soldering polar ear, makes lithium ion cell positive.
The preparation of negative pole: by graphite and conductive agent superconduction carbon (Super-P), thickener sodium carboxymethylcellulose (CMC), bonding agent butadiene-styrene rubber (SBR), solid-solid phase change material Cu-Si in mass ratio 95:1.5:1.5:1.0:1.0 make slurry, to be coated on copper foil of affluxion body and to dry at 80 DEG C; Carry out trimming, cut-parts, itemize, after itemize under vacuum 110 DEG C dry 5 hours, soldering polar ear, makes lithium ion battery negative.
The preparation of barrier film: barrier film is PP/PE/PP tri-layers of composite diaphragm, and thickness is 12 microns.
The preparation of electrolyte: by lithium hexafluoro phosphate (LiPF
6) be dissolved in the mixed solvent that ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) form (volume ratio of three is 2:1:1), obtain electrolyte.
The preparation of lithium ion battery: above-mentioned positive pole, barrier film and negative pole are wound into battery core, barrier film is between adjacent positive pole and negative pole, and positive pole is drawn with aluminium pole ears spot welding, and negative pole is drawn with the spot welding of nickel lug; Then battery core is placed in aluminium plastic packaging bag, injects above-mentioned electrolyte, through encapsulating, changing into, the operation such as capacity, make lithium ion battery.
Embodiment 2
As different from Example 1: in electrolyte, be added with inorganic solid-solid phase change material Li
2sO
4, all the other are with embodiment 1.
Embodiment 3
As different from Example 1: add organic solid-solid phase change material AMPD in electrolyte, all the other are with embodiment 1.
Embodiment 4
As different from Example 1: add organic solid-solid phase change material in barrier film and be cross-linked high density polyethylene (HDPE), all the other are with embodiment 1.
Embodiment 5
As different from Example 1: the Solid Organic solid phase change material that the outer surface of battery core positive pole, barrier film and negative pole are wound into pastes one deck insulation is cross-linked polyformaldehyde, and all the other are with embodiment 1.
Embodiment 6
As different from Example 1: the inorganic solid-solid phase change material Al-Si that positive pole adds is changed into and adds composite solid solid phase change material (10-C
10h
19nH
3)
2znCl, all the other are with embodiment 1.
Embodiment 7
As different from Example 1: the inorganic solid-solid phase change material Cu-Si that negative pole adds is changed into and adds composite solid solid phase change material (8-C
8h
15nH
3)
2cuCl, all the other are with embodiment 1.
Embodiment 8
As different from Example 1, the preparation of plus plate current-collecting body: first at surface-coated one deck solid-solid phase change material NH of aluminium foil
4sCN, and then hot pressing one deck aluminium foil, obtain the clad aluminum foil collector that tundish contains solid-solid phase change material, all the other are with embodiment 1.
Embodiment 9
As different from Example 1, the preparation of negative current collector: first at surface-coated one deck solid-solid phase change material KHF of Copper Foil
2, and then hot pressing one deck Copper Foil, obtain the composite copper foil collector that tundish contains solid-solid phase change material, all the other are with embodiment 1.
Embodiment 10
As different from Example 1: paste one deck solid-solid phase change material at the packaging material outer surface of lithium ion battery and be cross-linked high density polyethylene (HDPE), all the other are with embodiment 1.
Comparative example 1
The preparation of positive pole: by cobalt acid lithium (positive active material), conductive agent superconduction carbon (Super-P), bonding agent Kynoar (PVDF) in mass ratio 94:3.5:2.5 mix the lithium ion battery anode glue size made and there is certain viscosity, slurry is coated in current collector aluminum foil, colds pressing after drying at 80 DEG C; Then carry out trimming, cut-parts, itemize, after itemize under vacuum 80 DEG C dry 5 hours, soldering polar ear, makes lithium ion cell positive.
The preparation of negative pole: by graphite and conductive agent superconduction carbon (Super-P), thickener sodium carboxymethylcellulose (CMC), bonding agent butadiene-styrene rubber (SBR) in mass ratio 95:2.5:1.5:1.0 make slurry, to be coated on copper foil of affluxion body and to dry at 80 DEG C; Carry out trimming, cut-parts, itemize, after itemize under vacuum 110 DEG C dry 5 hours, soldering polar ear, makes lithium ion battery negative.
The preparation of barrier film: barrier film is PP/PE/PP tri-layers of composite diaphragm, and thickness is 12 microns.
The preparation of electrolyte: by lithium hexafluoro phosphate (LiPF
6) be dissolved in the mixed solvent that ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) form (volume ratio of three is 2:1:1), obtain electrolyte.
The preparation of lithium ion battery: above-mentioned positive pole, barrier film and negative pole are wound into battery core, barrier film is between adjacent positive pole and negative pole, and positive pole is drawn with aluminium pole ears spot welding, and negative pole is drawn with the spot welding of nickel lug; Then battery core is placed in aluminium plastic packaging bag, injects above-mentioned electrolyte, through encapsulating, changing into, the operation such as capacity, make lithium ion battery.
Comparative example 2
Paste unlike the outer surface of: battery core positive pole, barrier film and negative pole are wound into the solid-solid phase change material that one deck insulate with comparative example 1 and be cross-linked polyformaldehyde, all the other are with comparative example 1.
Battery temperature rise is tested:
Respectively battery temperature rise test is carried out to above-described embodiment 1 ~ 10 and comparative example 1 ~ 2.
Method of testing is as follows:
1), after electricity being full of according to 0.5C multiplying power to the battery of embodiment 1 ~ 10 and comparative example 1 ~ 2, shelving 1h and make battery recovery room temperature, after temperature stabilization, 5C multiplying power heavy-current discharge is carried out to above-mentioned battery;
2) to the maximum temperature that the both positive and negative polarity centre position of embodiment 1 ~ 10 and comparative example 1 ~ 2 is tested the temperature difference before and after its 5C multiplying power discharging and discharged when terminating 1min.
Gained test result is in table 1.
Table 1: battery temperature rise test experiments
Sequence number | The temperature difference (DEG C) | Maximum temperature (DEG C) |
Embodiment 1 | 18 | 58 |
Embodiment 2 | 16 | 50 |
Embodiment 3 | 12 | 54 |
Embodiment 4 | 10.2 | 49 |
Embodiment 5 | 9.8 | 52 |
Embodiment 6 | 8.8 | 48 |
Embodiment 7 | 11 | 56 |
Embodiment 8 | 8.0 | 46 |
Embodiment 9 | 8.2 | 47 |
Embodiment 10 | 10 | 52 |
Comparative example 1 | 35 | 85 |
Comparative example 2 | 25 | 70 |
As can be seen from the above table, the temperature rise that the temperature rise ratio of lithium ion battery of adding solid-solid phase change material does not add the battery of solid-solid phase change material reduces about 15 DEG C, and maximum temperature is low about 20 DEG C simultaneously.Visible, by adding solid-solid phase change material in the inside of lithium ion battery or outside, the high temperature performance of lithium ion battery is effectively improved; And at inside battery and the outside temperature control effect adding solid-solid phase change material simultaneously than only the independent temperature control effect added at outside batteries is good.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change above-mentioned execution mode and revise.Therefore, the present invention is not limited to above-mentioned embodiment, and any apparent improvement of every those skilled in the art done by basis of the present invention, replacement or modification all belong to protection scope of the present invention.In addition, although employ some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (8)
1. one kind possesses the lithium ion battery of temp regulating function, comprise positive pole, negative pole and to be interposed between the battery core of the membrane winding between described positive pole and described negative pole, and electrolyte, it is characterized in that: also comprise solid-solid phase change material, described solid-solid phase change material is added at least one place of described positive pole, described negative pole, described barrier film, described electrolyte.
2. the lithium ion battery possessing temp regulating function according to claim 1, is characterized in that: described solid-solid phase change material is covered on the outer surface of described battery core.
3. the lithium ion battery possessing temp regulating function according to claim 1 and 2, is characterized in that: the phase transition temperature range of described solid-solid phase change material is-40 DEG C ~ 150 DEG C.
4. the lithium ion battery possessing temp regulating function according to claim 3, is characterized in that: the phase transition temperature range of described solid-solid phase change material is-20 DEG C ~ 85 DEG C.
5. the lithium ion battery possessing temp regulating function according to claim 1, is characterized in that: described solid-solid phase change material comprises at least one of organic solid-solid phase change material, inorganic solid-solid phase change material, composite solid solid phase change material.
6. the lithium ion battery possessing temp regulating function according to claim 5, it is characterized in that: described Solid Organic solid phase change material is at least one in crosslinked high density polyethylene (HDPE), crosslinked polyformaldehyde, pentaerythrite, neopentyl glycol, dihydroxymethyl ethane, AMPD and trishydroxymethylaminomethane.
7. the lithium ion battery possessing temp regulating function according to claim 5, is characterized in that: described inorganic solid-solid phase change material is NH
4sCN, Li
2sO
4, KHF
2, at least one in Al-Si, Cu-Si.
8. the lithium ion battery possessing temp regulating function according to claim 5, is characterized in that: described composite solid solid phase change material is (n-C
nh
2n-1nH
3)
2mX
1, wherein: X is chlorine, n is carbon number (n=8 ~ 18), and M is any one in Mn, Cu, Fe, Cd, Ni, Zn, Co.
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Cited By (12)
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CN106207237A (en) * | 2016-08-29 | 2016-12-07 | 重庆大学 | There is the Proton Exchange Membrane Fuel Cells of cold-starting function |
CN106972194A (en) * | 2017-04-21 | 2017-07-21 | 天津力神电池股份有限公司 | A kind of lithium ion battery |
CN107946487A (en) * | 2017-11-15 | 2018-04-20 | 江苏华富储能新技术股份有限公司 | A kind of storage battery protective housing containing phase-changing energy storage material |
CN107968159A (en) * | 2017-11-15 | 2018-04-27 | 江苏华富储能新技术股份有限公司 | A kind of high-low temperature resistant lead accumulator containing phase-changing energy storage material |
CN107994191A (en) * | 2017-11-15 | 2018-05-04 | 江苏华富储能新技术股份有限公司 | A kind of AGM partition plates for lead accumulator containing phase-changing energy storage material |
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CN112812746A (en) * | 2021-01-04 | 2021-05-18 | 华鼎国联动力电池有限公司 | Solid-solid composite phase change material and method for reducing temperature rise of lithium ion battery |
CN112825620A (en) * | 2019-09-19 | 2021-05-21 | 株式会社Lg化学 | Electrode current collector comprising hot-pressed conversion layer between two or more metal foils, electrode comprising same, and lithium secondary battery |
CN113328154A (en) * | 2020-02-28 | 2021-08-31 | 北京小米移动软件有限公司 | Lithium battery, mobile terminal and temperature control method of lithium battery |
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CN106972194A (en) * | 2017-04-21 | 2017-07-21 | 天津力神电池股份有限公司 | A kind of lithium ion battery |
CN107946487A (en) * | 2017-11-15 | 2018-04-20 | 江苏华富储能新技术股份有限公司 | A kind of storage battery protective housing containing phase-changing energy storage material |
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CN112825620A (en) * | 2019-09-19 | 2021-05-21 | 株式会社Lg化学 | Electrode current collector comprising hot-pressed conversion layer between two or more metal foils, electrode comprising same, and lithium secondary battery |
CN113328154A (en) * | 2020-02-28 | 2021-08-31 | 北京小米移动软件有限公司 | Lithium battery, mobile terminal and temperature control method of lithium battery |
WO2021251682A1 (en) * | 2020-06-08 | 2021-12-16 | 주식회사 엘지에너지솔루션 | Electrode assembly and secondary battery comprising same |
CN112812746A (en) * | 2021-01-04 | 2021-05-18 | 华鼎国联动力电池有限公司 | Solid-solid composite phase change material and method for reducing temperature rise of lithium ion battery |
CN114023923A (en) * | 2021-11-03 | 2022-02-08 | 天津市捷威动力工业有限公司 | Negative pole piece, lithium ion battery, and preparation method and application of negative pole piece and lithium ion battery |
CN114023923B (en) * | 2021-11-03 | 2023-10-13 | 天津市捷威动力工业有限公司 | Negative electrode plate, lithium ion battery, and preparation method and application of negative electrode plate and lithium ion battery |
CN117766908A (en) * | 2023-12-11 | 2024-03-26 | 武汉理工大学 | Low-temperature heat management system and battery of solid-solid composite phase change material embedded lithium battery |
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