WO2022261876A1 - Electrochemical apparatus and secondary battery - Google Patents
Electrochemical apparatus and secondary battery Download PDFInfo
- Publication number
- WO2022261876A1 WO2022261876A1 PCT/CN2021/100449 CN2021100449W WO2022261876A1 WO 2022261876 A1 WO2022261876 A1 WO 2022261876A1 CN 2021100449 W CN2021100449 W CN 2021100449W WO 2022261876 A1 WO2022261876 A1 WO 2022261876A1
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- Prior art keywords
- heat
- heating
- soaking
- electrochemical device
- temperature
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- H01M10/654—Means for temperature control structurally associated with the cells located inside the innermost case of the cells, e.g. mandrels, electrodes or electrolytes
-
- 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
Definitions
- the present application relates to the field of battery technology, in particular to an electrochemical device and a secondary battery capable of achieving rapid heating and uniform heat generation.
- the use of lithium-ion batteries is greatly affected by temperature.
- the electronic conductance and ion conductance are affected, and the kinetic performance drops sharply, which leads to lithium precipitation in the lithium-ion battery during high-rate charging, deteriorating the battery interface, and posing a safety risk.
- the capacity of battery active materials is affected, and the voltage platform drops, resulting in a loss of battery energy density.
- Heating the battery and heating the battery to room temperature can prevent the battery from being used in low temperature scenarios. This method does not need to change the chemical system, which can effectively improve the battery dynamics, and at the same time can broaden the temperature range of the lithium battery, and realize the normal charging of the battery in an extremely low temperature environment , and maintain the same charging rate as charging at room temperature.
- the advantage of the method of heating up the battery with the built-in heating sheet is that the heating rate is fast, and a heating rate of 1°C/s can be achieved.
- the existing heating sheets are packaged with insulating materials with consistent thermal conductivity, they do not have the ability to uniform temperature. When the heating sheet is placed inside the cell, the heat generation and heat dissipation capabilities of different parts are different, resulting in the temperature of the cell The distribution is uneven, as shown in Figure 1.
- the heating sheet when the heating sheet is packaged with an insulating and heat-conducting material with consistent thermal conductivity, after the built-in heating sheet of the cell is heated at a rate of 0.5°C/s for 1 minute, the temperature difference between the area with the highest temperature on the surface of the cell and the lowest temperature can reach more than 10°C .
- the faster the heating plate heating rate the greater the temperature difference between different parts. Excessive local temperature will aggravate the internal side reactions of the battery, and there will be risks such as thermal runaway, which will lead to deterioration of battery performance and safety problems. Therefore, it is necessary to further improve the temperature uniformity of the materials on both sides of the heating plate, reduce the temperature difference of the battery core, and improve the reliability of the battery.
- related technologies for improving battery temperature uniformity include: (1) setting a heat conduction layer or a heat dissipation layer on the battery casing, which can speed up the thermal diffusion on the surface of the battery cell, but still cannot improve the temperature inside the battery cell.
- the uniformity of temperature distribution cannot solve the problems of local heat accumulation inside the battery; (2) Adding a vapor chamber inside the cell can only improve the uniformity of temperature distribution inside the cell to a certain extent, because it does not directly improve
- the uniformity of heat production of the heating sheet itself when the battery has a built-in heating sheet that can quickly heat up, the temperature equalization effect of the soaking plate is not ideal, and it mainly accelerates the heat dissipation of the battery, and cannot make full use of the heat generated by the heating sheet itself. That is, it is impossible to promote the conduction of heat from the parts with high heat generation to the parts with low heat generation, so that the heating sheet itself can not only heat up quickly but also produce heat evenly.
- the purpose of this application is to provide an electrochemical device to solve the problem of uneven heat generation and heat dissipation on the surface of the heating sheet when the heating sheet is heated rapidly when the heating sheet built in the existing electric core is packaged with a uniform thermal conductivity insulating material, thereby Causes the problem of uneven temperature inside the battery cell.
- an electrochemical device which includes a heating assembly, and the heating assembly includes a heating part and a heat equalizing part arranged around the heating part.
- the heat equalizing portion includes a first heat equalizing portion and a second heat equalizing portion that do not overlap each other, and the ratio of the reciprocal of the thermal resistance of the first heat equalizing portion to the second heat equalizing portion is greater than or equal to 1.05, so The areas of the first heat soaking portion and the second heat soaking portion are respectively greater than 2 cm 2 .
- the ratio of the reciprocal of the thermal resistance of the first heat soaking part to the second heat soaking part is preferably greater than 1.2.
- the ratio of the reciprocal of the thermal resistance of the first heat soaking part to the second heat soaking part is greater than 1.6. In one embodiment, the ratio of the reciprocal of the thermal resistance of the first heat soaking part to the second heat soaking part is greater than 1.75.
- the built-in heating components are packaged with heat-spreading parts (insulating materials) with different heat conduction capabilities, and the heat-generating parts of the heating parts with low heat generation and low temperature are packaged with heat-spreading parts with high heat conduction capabilities.
- Heat part (insulation material) package use heat soaking part (insulation material) package with low thermal conductivity in the part with high heat generation and high temperature, which can reduce the heat generation part along the Z direction (inside the heating part to the heat soaking part) Surface direction, that is, the thickness direction of the heating component, that is, the thickness direction of the electrochemical device), and under the action of temperature difference, it will promote a part of the heat to pass through the heating part along the X direction (the length direction of the heating component, that is, the electrical The length direction of the chemical device) and the Y direction (the width direction of the heating component, that is, the width direction of the electrochemical device) conduct to the low temperature part, thereby increasing the temperature of the low temperature part, thereby improving the temperature uniformity of the electrochemical device .
- the X direction the length direction of the heating component, that is, the electrical The length direction of the chemical device
- the Y direction the width direction of the heating component, that is, the width direction of the electrochemical device
- the resistivity of the heating part ranges from 10 -8 ⁇ m to 10 -5 ⁇ m, and the thickness of the heating part ranges from 1 ⁇ m to 80 ⁇ m.
- the resistivity of the material of the heating part should not be too large, otherwise it will easily lead to the problem of uneven local heat; the resistivity of the material of the heating part should not be too small to ensure the heating efficiency of the heating part.
- the thickness of the heating part should not be too large to ensure the heating efficiency of the heating part and the energy density of the electrochemical device; the thickness of the heating part should not be too small to ensure that the heating part has high electron conductivity and current carrying capacity, so that it can Ensure the heating function of the heating part.
- the thermal conductivity of the heat soaking portion ranges from 0.1 W/m ⁇ K to 100 W/m ⁇ K, and the thickness of the heat soaking portion ranges from 1 ⁇ m to 80 ⁇ m.
- the thickness of the soaking part should not be too large to ensure the energy density of the electrochemical device; the thickness of the soaking part should not be too small to ensure that it has a certain mechanical strength and protective effect, and can ensure that the heating part will not interfere with the electrochemical device
- the pole piece is directly connected, causing failure.
- the heating part may have a certain pattern.
- the pattern of the heating part includes at least one of a square wave pattern, a zigzag pattern, a zigzag pattern, and a water wave pattern.
- the heat soaking part includes a first heat soaking part, a second heat soaking part ... and an Nth heat soaking part, wherein N is an integer greater than or equal to 3, and the thermal resistance of the first heat soaking part
- the material of the heating part includes at least one of metal material, carbon-based conductive material, metal oxide or conductive polymer material.
- the metal material includes nickel, titanium, copper, gold, silver, platinum, iron, cobalt, chromium, tungsten, molybdenum, aluminum, magnesium, potassium, sodium, calcium, strontium, barium, silicon, germanium , antimony, lead, indium, zinc, or at least one of a combination of these elements.
- the carbon-based conductive material includes at least one of carbon black, graphite, graphene, carbon fiber, single-walled carbon nanotubes, or multi-walled nanotubes.
- the metal oxide includes aluminum-doped zinc oxide, calcium-doped lanthanum chromate, tin dioxide, fluorine-doped tin dioxide, antimony-doped tin dioxide, indium tin oxide, silver-doped indium tin oxide, or At least one of silver alloy indium tin oxide.
- the conductive polymer material includes at least one of polyacetylene, polypyrrole, polythiophene, polyparaphenylene, polyphenylene vinylene, polyaniline or its doped polymer material, and the doped high Dopants in molecular materials include chlorine, iodine, bromine, iodine chloride, iodine bromide, iodine fluoride, phosphorus pentafluoride, hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, molybdenum pentafluoride, At least one of tungsten pentafluoride, titanium tetrachloride, zirconium tetrachloride, ferric chloride or tin tetraiodide.
- the material of the soaking part includes thermally conductive silicone grease, silica gel, thermally conductive putty, potting glue, ABS plastic, soft and hard PVC, paraffin, asbestos, hardwood, cork, UP resin, organic glass , polycarbonate, nylon, polyethylene, polypropylene, isobutylene, polyamide, polyimide, polysulfide, polyester resin, polyurethane resin, neoprene, polyester mohair, elastomeric foam, polyurethane , epoxy resin, polyphenylene sulfide plastic, polyamide, graphite, aluminum oxide, magnesium oxide, zinc oxide or nickel oxide.
- the heating assembly includes a first tab and a second tab, the first tab and the second tab are both arranged on the heating part, and are connected to the heating part electrical connection.
- the electrochemical device further includes a positive pole piece and a negative pole piece, and the heating assembly is in contact with the positive pole piece or the negative pole piece.
- the present application also provides a secondary battery, which includes the above-mentioned electrochemical device, a temperature sensing device, and a control system connected with the temperature sensing device and the heating assembly, the control system According to the temperature detected by the temperature sensing device, the circuit where the heating component is located can be controlled to be on or off.
- control system can control the circuit where the heating component is located to be on or off according to the temperature detected by the temperature sensing device and the set target temperature T.
- the control system reads the temperature detected by the temperature sensing device, and when the detected temperature is lower than the target temperature T, the circuit is in a conducting state, and the current passes through the heating component to heat The component realizes the heating function of the electrochemical device.
- the control system controls the circuit to be disconnected, and the heating component stops heating.
- control system reads the temperature of the electrochemical device, and when the temperature of the electrochemical device is greater than or equal to T, the circuit is in an open state.
- the heating component when the circuit is on, the heating component is powered by an electrochemical device or an external power supply, and the heating component is in a working mode; when the circuit is off, the heating component does not generate heat.
- the built-in heating components are packaged with insulating materials with different thermal conductivity according to the temperature distribution characteristics of the surface.
- the parts with low heat generation and low temperature in the heating part of the heating element are packaged with insulating material with high thermal conductivity, and the parts with high heat generation and high temperature are packaged with materials with low heat conductivity, which can reduce the position of high heat generation along the Z direction (heating part to the surface of the heat soaking part, that is, the thickness direction of the heating assembly, that is, the thickness direction of the electrochemical device), and under the action of the temperature difference, a part of the heat will be promoted to pass through the heating part along the X direction (heating The length direction of the assembly (that is, the length direction of the electrochemical device) and the Y direction (the width direction of the heating assembly, that is, the width direction of the electrochemical device) are conducted to the low temperature part, thereby increasing the temperature of the low temperature part.
- the electrochemical device provided by this application can make full use of the heat generated by the heating part, effectively reduce the temperature difference on the surface of the heating part, realize the uniform heat generation of the heating component, and finally realize the rapid heating of the electrochemical device while improving the performance of the electrochemical device. temperature uniformity.
- Fig. 1 is a diagram of the temperature distribution on the surface of the battery cell when the built-in heating sheet is heated in the prior art.
- Fig. 2 is a schematic diagram of an electrochemical device provided by one or several embodiments of the present application.
- Fig. 3 is a schematic diagram of a heating assembly provided in one or several embodiments of the present application.
- Fig. 4 is a schematic diagram of a heating assembly provided in one or several embodiments of the present application.
- Fig. 5 is a schematic diagram of a heating part provided in one or several embodiments of the present application.
- spatially relative terms such as “on” and the like may be used herein for convenience of description to describe the relationship of one element or feature to another element(s) or feature(s) as illustrated in the figures. It will be understood that spatially relative terms are intended to encompass different orientations of the device or device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “above” or “on” other elements or features would then be oriented “below” or “beneath” the other elements or features. Thus, the exemplary term “on” can encompass both an orientation of above and below.
- first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections do not shall be limited by these terms. These terms are used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the example embodiments.
- the thickness direction of the heating assembly (the thickness direction of the electrochemical device) is defined as the Z direction
- the longitudinal direction of the heating assembly (the length direction of the electrochemical device) is defined as the X direction
- the width direction of the heating assembly (the electrochemical device) is defined as the X direction.
- the width direction) is the Y direction.
- the insulating material (soaking part) with a larger reciprocal value is used to encapsulate the heating part, and the insulating material (soaking part) with a smaller reciprocal value of thermal resistance is used to encapsulate the heating part at the part with a higher temperature.
- the present application provides an electrochemical device 100 , and the electrochemical device 100 includes a heating component 10 .
- the heating assembly 10 includes a heating part 11 and a heat soaking part 12 disposed around the heating part 11 , that is, the surface of the heating part 11 is covered by the heat soaking part 12 .
- the heat equalizing portion 12 includes a first heat equalizing portion 121 and a second heat equalizing portion 122 that do not overlap each other, and the ratio of the reciprocal of the thermal resistance of the first heat equalizing portion 121 to the second heat equalizing portion 122 is greater than Or equal to 1.05, the areas of the first heat equalizing portion 121 and the second heat equalizing portion 122 are respectively greater than 2 cm 2 .
- the ratio of the reciprocal of the thermal resistance of the first heat equalizing portion 121 and the second heat equalizing portion 122 is preferably greater than 1.2. In some embodiments, the ratio of the reciprocal of the thermal resistance of the first heat-spreading portion 121 and the second heat-spreading portion 122 is greater than 1.6. In some embodiments, the ratio of the reciprocal of the thermal resistance of the first heat-spreading portion 121 and the second heat-spreading portion 122 is greater than 1.75.
- the temperature of the electrochemical device decreases gradually from bottom to top (the position where the tab 200 is located is the top).
- the heating part 11 is packaged with the first heat soaking part 121 with a relatively large reciprocal of the thermal resistance value at the lower temperature part of the heating part 11, and the thermal The second heat soaking part 122 with the smallest reciprocal resistance is packaged on the heating part 11, which can reduce the heat conduction ability of the part with a higher temperature on the heating part 11 along the Z direction, and under the action of the temperature difference, a part of the heat will be promoted along the X direction and The Y-direction conducts toward the lower temperature area, thereby increasing the temperature of the lower temperature area.
- the area of the soaking portion is the projected area of the soaking portion along the thickness direction Z direction
- the thickness L of the soaking portion is measured by a vernier caliper
- a single area (for example, a diameter of 25mm) measures multiple points (4 above) and take the average value.
- the thermal conductivity is measured by the following method: a thermal conductivity meter (such as Unitherm TM 2022) is used for measurement, and the sample is placed between two surface-polished metal plates (ie, an upper plate and a lower plate), and the upper plate and the lower plate are respectively Controlled at different temperatures, the lower surface of the lower plate is a calibrated heat flow sensor; when a certain temperature difference is maintained between the upper surface and the lower surface of the sample to achieve thermal equilibrium, a longitudinal heat flow passing through the sample from top to bottom is generated; through The thermal conductivity coefficient can be calculated by measuring the temperature difference between the upper and lower surfaces of the sample (the temperature difference between the upper and lower surfaces of the sample is measured by a temperature sensor placed on the surface of the high thermal conductivity metal at the upper and lower ends of the sample), the reading of the heat flow sensor and the known thickness of the sample.
- a thermal conductivity meter such as Unitherm TM 2022
- the heat equalizing portion 12 includes a first heat equalizing portion 121, a second heat equalizing portion 122... and an Nth heat equalizing portion, wherein N is an integer greater than or equal to 3, and the first heat equalizing portion 121
- the heat soaking part 12 includes a first heat soaking part 121 , a second heat soaking part 122 and a third heat soaking part 123 , and the reciprocal of the thermal resistance of the first heat soaking part 121 > the second heat soaking part
- the heat conduction capacity of the first heat equalization part 121 is greater than the heat conduction capacity of the second heat equalization part 122
- the heat conduction capacity of the second heat equalization part 122 is greater than the heat conduction capacity of the third heat equalization part 123
- the heat conduction capability of the N-1th heat soaking part is greater than the heat conduction capability of the Nth heat soaking part
- the heat conduction capability refers to the reciprocal of the thermal resistance value of the heat soaking part per unit area.
- first heat soaking part 121, the second heat soaking part 122, and the third heat soaking part 123 can divide the area of the heat soaking part and the material of the heat soaking part according to the temperature distribution of the heating part and the electric core during operation. choose.
- the resistivity of the heating part 11 ranges from 10 -8 ⁇ m to 10 -5 ⁇ m, and the thickness of the heating part 11 is 1 ⁇ m to 80 ⁇ m.
- the thickness of the heating part 11 should not be too large to ensure the heating efficiency of the heating part 11 and the energy density of the electrochemical device 100; the thickness of the heating part 11 should not be too small to ensure that the heating part 11 has a higher electron conductivity and load capacity. flow capacity, so that the heating function of the heating part 11 can be ensured.
- the heating part 11 may have a certain pattern. In some embodiments, the heating portion has a square wave pattern. In some embodiments, the heating part may also have other patterns such as zigzagging, zigzag, and water waves. It can be understood that the shape of the heating part, the width of the material, etc. can be designed according to the shape of the cell and the temperature distribution, so as to ensure sufficient heating of the electrochemical device 100 by the heating part 11 .
- the thermal conductivity of the heat soaking portion 12 ranges from 0.1 W/m ⁇ K to 100 W/m ⁇ K, and the thickness of the heat soaking portion 12 ranges from 1 ⁇ m to 80 ⁇ m.
- the thickness of the soaking part 12 should not be too large, so as to ensure the energy density of the electrochemical device 100; The pole pieces of the electrochemical device 100 are directly connected, causing failure.
- the material of the heating part 11 includes at least one of metal material, carbon-based conductive material, metal oxide or conductive polymer material.
- the metal material includes nickel (Ni), titanium (Ti), copper (Cu), gold (Au), silver (Ag), platinum (Pt), iron (Fe), cobalt (Co), chromium ( Cr), tungsten (W), molybdenum (Mo), aluminum (Al), magnesium (Mg), potassium (K), sodium (Na), calcium (Ca), strontium (Sr), barium (Ba), silicon ( At least one of Si), germanium (Ge), antimony (Sb), lead (Pb), indium (In), zinc (Zn) and combinations (alloys) thereof.
- the carbon-based conductive material includes at least one of carbon black, graphite, graphene, carbon fiber, single-walled carbon nanotubes or multi-walled nanotubes.
- the metal oxide includes aluminum-doped zinc oxide, calcium-doped lanthanum chromate, tin dioxide, fluorine-doped tin dioxide, antimony-doped tin dioxide, indium tin oxide, silver-doped indium tin oxide or silver-doped alloy oxide at least one of indium tin.
- the conductive polymer material includes at least one of polyacetylene, polypyrrole, polythiophene, polyparaphenylene, polyphenylene vinylene, polyaniline or its doped polymer material, and the doped polymer material
- Dopants include chlorine, iodine, bromine, iodine chloride, iodine bromide, iodine fluoride, phosphorus pentafluoride, hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, molybdenum pentafluoride, pentafluoride At least one of tungsten, titanium tetrachloride, zirconium tetrachloride, ferric chloride or tin tetraiodide.
- the material of the heat equalizing part 12 is an insulating material with thermal conductivity, including thermal conductive silicone grease, silica gel, thermal conductive paste, potting glue, ABS plastic, soft and hard PVC (polyvinyl chloride), Paraffin, asbestos, hardwood, cork, UP resin (unsaturated polyester), plexiglass (PMMA), polycarbonate, nylon, polyethylene, polypropylene (PP), isobutylene, polyamide (PA), polyimide (PI), polysulfide, polyester resin, polyurethane resin, neoprene (PCP), polyester mohair, elastomeric foam, polyurethane, epoxy resin, polyphenylene sulfide plastic, polyamide, graphite, At least one of aluminum oxide (Al 2 O 3 ), magnesium oxide (MgO), zinc oxide (ZnO) or nickel oxide (NiO).
- Al 2 O 3 At least one of aluminum oxide (Al 2 O 3 ), magnesium oxide (MgO), zinc oxide (ZnO) or nickel
- the heating assembly 10 includes a first tab 13 and a second tab 14 .
- both the first tab 13 and the second tab 14 are disposed on the heating portion 11 and are electrically connected to the heating portion 11 .
- the electrochemical device further includes a positive pole piece and a negative pole piece, and the heating assembly is in contact with at least one of the positive pole piece or the negative pole piece.
- a nickel tab is welded on the left and right sides of the copper sheet, that is, the first tab 13 and the second tab 14 .
- the first heat soaking part 121 uses high density polyethylene (thermal conductivity: 0.4W/m ⁇ K-0.5W/m ⁇ K) to heat seal the copper sheet
- the second heat soaking part 122 uses low Density polyethylene (thermal conductivity: 0.2-0.3 W/m ⁇ K) is heat-sealed, and the thickness of the first heat soaking part 121 and the second heat soaking part 122 are the same, both being 10 ⁇ m.
- the first heat equalizing portion 121 and the second heat equalizing portion 122 surround the copper sheet, ie a heating assembly is obtained.
- the positive electrode active material layer of the pole piece is cold-pressed to a compaction density of 4.0g/cm 3 , followed by auxiliary processes such as tab welding and adhesive paper, that is, the double-sided coated positive pole piece is completed the entire preparation process.
- the negative electrode active material layer of the pole sheet is cold-pressed to a compacted density of 1.7 g/cm 3 .
- Subsequent auxiliary processes such as tab welding and sticking paper are carried out, that is, the entire preparation process of the double-sided coated negative electrode sheet is completed.
- EC organic solvent
- EMC ethyl methyl carbonate
- DEC diethyl carbonate
- Polyethylene (PE) with a thickness of 15 ⁇ m was selected as the separator, and the prepared positive electrode sheet, heating assembly, separator, and negative electrode sheet were stacked in order and wound into a battery core.
- the heating assembly was located in the electrochemical device.
- the winding center is the winding head of the battery core. After top sealing and side sealing, the cell is then injected with liquid, and the cell after liquid injection is formed (0.02C constant current charging to 3.3V, and then 0.1C constant current charging to 3.6V), and finally the electrochemical cell is obtained. device.
- an external power supply applies a certain current to the first lug 13 and the second lug 14 of the heating assembly 10 to start heating.
- the heating power is 15W, heat for 1min, or when the heating power is 8W, heat for 2min. .
- the temperature distribution on the surface of the electrochemical device is collected.
- the temperature distribution can be measured by two methods: the first is direct contact method for point-by-point temperature measurement, such as thermocouples, and then obtain the required temperature field distribution information through statistical methods; the other method is to use infrared thermal imaging
- the instrument is used to measure the maximum temperature difference on the surface of the electrochemical device.
- step (1) the first soaking part 121 is made of low-density polyethylene (thermal conductivity: 0.2-0.3 W/m K), and the second soaking part 122 is made of low-density silica gel ( Thermal conductivity: 0.12W/m ⁇ K).
- step (1) the thickness of the second soaking portion is 20 ⁇ m.
- step (1) the copper sheet (heating part 11 ) is heat-sealed with high-density polyethylene (thermal conductivity: 0.4-0.5 W/m ⁇ K) with a thickness of 10 ⁇ m.
- step (1) the copper sheet (heating part 11 ) is heat-sealed with low-density silica gel (thermal conductivity: 0.12 W/m ⁇ K) with a thickness of 10 ⁇ m.
- the heat soaking part 12 includes three packaging areas, namely the first heat soaking part 121, the second heat soaking part 122 and the third heat soaking part 123.
- the first heat soaking part 121 adopts high-density polyethylene (thermal conductivity: 0.4-0.5W/m K)
- the second heat soaking part 122 adopts polyimide (PI) (thermal conductivity: 0.3-0.4W/m K).
- the third heat equalization part 123 is made of low-density polyethylene (thermal conductivity: 0.2-0.3 W/m ⁇ K)
- the thickness of the three packaging regions is the same, all of which are 10 ⁇ m.
- step (1) the packaging material of the first soaking portion 121 is silica gel (thermal conductivity: 0.35W/m ⁇ K), and the packaging material of the second soaking portion 122 is low-density polystyrene. Ethylene (thermal conductivity: 0.2-0.3W/m ⁇ K), and the packaging material of the third soaking portion 123 is low-density silica gel (thermal conductivity: 0.12W/m ⁇ K).
- step (1) the thickness of the second heat soaking portion 122 is 15 ⁇ m, and the thickness of the third heat soaking portion 123 is 20 ⁇ m.
- the difference with Embodiment 1 is: in step (1), the first heat equalizing portion 121 and the second heat equalizing portion 122 are all made of high-density polyethylene (thermal conductivity: 0.4W/m K-0.5W/m K , thickness 10 ⁇ m) after packaging, the second heat soaking part 122 is packaged with a layer of low-density polyethylene (thermal conductivity: 0.2-0.3 W/m ⁇ K), thickness 10 ⁇ m, therefore, after the packaging is completed by heat sealing, Finally, the package thickness of the first heat soaking portion 121 is 10 ⁇ m, and the thickness of the second heat soaking portion 122 is 20 ⁇ m (10 ⁇ m+10 ⁇ m).
- step (1) the heating part 11 is made of nickel sheet.
- step (1) the thickness of the heating part 11 is 30 ⁇ m.
- step (6) the heating mode of the heating part 11 is changed to an internal power supply, that is, the control circuit in the electrochemical device is in a conduction state, and the first tab 13 and the second tab 14 respectively pass through
- the control circuit is electrically connected to the positive pole lug and the negative pole pole lug in the electrochemical device, and the heating function of the heating part is realized by applying an electric current inside the electrochemical device.
- step (5) the cell is prepared in the form of lamination.
- Example 1 The parameter settings and test results of Example 1, Example 11 and Comparative Example 1 are shown in Table 7.
- the heating part with high heat generation and high temperature is used in this application.
- High-performance insulating material packaging the heating part with low heat generation and low temperature is packaged with insulating material with high thermal conductivity, making full use of the heat generation of the heating part itself, which can promote heat conduction from the high temperature part of the heating part itself to the low temperature part , which in turn can effectively reduce the maximum temperature difference on the surface of the electrochemical device, that is, effectively improve the problem of uneven temperature of the electrochemical device.
- the built-in heating components are packaged with insulating materials with different thermal conductivity according to the temperature distribution characteristics of the surface.
- the parts with low heat generation and low temperature of the heating part of the heating element are packaged with insulating materials with high thermal conductivity, and the parts with high heat generation and high temperature are packaged with materials with low thermal conductivity, which can reduce the parts with high heat generation along the Z-axis Direction (the inside of the heating part to the surface of the heat soaking part, that is, the thickness direction of the electrochemical device), and under the action of temperature difference, it will promote a part of the heat to pass through the heating part along the X-axis direction (the length of the electrochemical device) direction) and the Y-axis direction (the width direction of the electrochemical device) conduct toward the low-temperature part, thereby increasing the temperature of the low-temperature part.
- the electrochemical device provided by the present application can make full use of the heat generated by the heating part, effectively reduce the temperature difference on the surface of the heating part, and finally achieve rapid
Abstract
Provided in the present application are an electrochemical apparatus and a secondary battery. The electrochemical apparatus comprises a heating assembly, wherein the heating assembly comprises a heating portion, and a soaking portion, which is arranged around the heating portion; the soaking portion comprises a first soaking portion and a second soaking portion, which do not overlap with each other; the ratio of reciprocals of thermal resistance values of the first soaking portion and the second soaking portion is greater than or equal to 1.05; and the area of the first soaking portion and the area of the second soaking portion are each greater than 2 cm2. By means of the electrochemical apparatus provided in the present application, heat generated by a heating portion can be fully utilized, thereby effectively reducing the temperature difference of the surface of the heating portion, finally realizing a rapid temperature rise and uniform heat generation of the heating portion, and further improving the temperature uniformity of the electrochemical apparatus.
Description
本申请涉及电池技术领域，尤其涉及一种可实现快速升温和均匀产热的电化学装置及二次电池。The present application relates to the field of battery technology, in particular to an electrochemical device and a secondary battery capable of achieving rapid heating and uniform heat generation.
众所周知，锂离子电池的使用受温度影响较大。通常在低温环境中对其进行充电时，电子电导和离子电导受到影响，动力学性能急剧下降，导致锂离子电池在大倍率充电过程中出现析锂，恶化电池界面，存在安全风险。同时，在低温环境中，电池活性材料容量发挥受到影响，电压平台下降，使得电池能量密度受到损失。对电池进行加热，将电池加热至常温可以避免电池在低温场景使用，该方法无需更改化学体系，可有效提升电池动力学，同时可以拓宽锂电池使用温度范围，实现极低温环境下电池的正常充电，并且和常温充电时保持相同的充电倍率。As we all know, the use of lithium-ion batteries is greatly affected by temperature. Usually, when it is charged in a low-temperature environment, the electronic conductance and ion conductance are affected, and the kinetic performance drops sharply, which leads to lithium precipitation in the lithium-ion battery during high-rate charging, deteriorating the battery interface, and posing a safety risk. At the same time, in a low temperature environment, the capacity of battery active materials is affected, and the voltage platform drops, resulting in a loss of battery energy density. Heating the battery and heating the battery to room temperature can prevent the battery from being used in low temperature scenarios. This method does not need to change the chemical system, which can effectively improve the battery dynamics, and at the same time can broaden the temperature range of the lithium battery, and realize the normal charging of the battery in an extremely low temperature environment , and maintain the same charging rate as charging at room temperature.
电芯内置加热片升温的方法优点是加热速率快，可实现1℃/s的升温速率。但由于现有的加热片都是采用导热能力一致的绝缘材料进行封装，不具备均温能力，当加热片置于电芯内部时，不同部位的产热和散热能力存在差异，导致电芯温度分布不均匀，如图1所示。例如，当对加热片使用导热能力一致的绝缘导热材料封装时，电芯内置的加热片以0.5℃/s速率加热1min后，电芯表面温度最高的区域与温度最低的温差可达10℃以上。加热片升温速率越快时，不同部位的温差越大。局部温度过高会加剧电芯内部副反应，存在热失控等风险，导致电芯性能恶化且存在安全问题。因此需进一步改善加热片两侧材料的均温能力，降低电芯温差，提升电池的可靠性。The advantage of the method of heating up the battery with the built-in heating sheet is that the heating rate is fast, and a heating rate of 1°C/s can be achieved. However, because the existing heating sheets are packaged with insulating materials with consistent thermal conductivity, they do not have the ability to uniform temperature. When the heating sheet is placed inside the cell, the heat generation and heat dissipation capabilities of different parts are different, resulting in the temperature of the cell The distribution is uneven, as shown in Figure 1. For example, when the heating sheet is packaged with an insulating and heat-conducting material with consistent thermal conductivity, after the built-in heating sheet of the cell is heated at a rate of 0.5°C/s for 1 minute, the temperature difference between the area with the highest temperature on the surface of the cell and the lowest temperature can reach more than 10°C . The faster the heating plate heating rate, the greater the temperature difference between different parts. Excessive local temperature will aggravate the internal side reactions of the battery, and there will be risks such as thermal runaway, which will lead to deterioration of battery performance and safety problems. Therefore, it is necessary to further improve the temperature uniformity of the materials on both sides of the heating plate, reduce the temperature difference of the battery core, and improve the reliability of the battery.
现有技术中，关于改善电池均温性能的相关技术包括：(1)在电池壳体上设置导热层或散热层，该方法可加快电芯表面的热扩散，但仍无法改善电芯内部的温度分布均匀性，无法解决电池内部的局部热聚集等问题；(2)在电芯内部增加均热板，该方法只能在一定程度上改善电芯内部的温度分布均匀性，由于并非直接改善加热片本身的产热均匀性，当电芯内置可快速升温的加热片时，采用均热板的方法均温效果不理想，且主要加快了电池散热，不能充分利用加热片本身的产热，即无法促进加热片本身产热高的部位向产热低的部位传导热，从而无法实 现加热片本身既要快速升温又要均匀产热的需求。In the prior art, related technologies for improving battery temperature uniformity include: (1) setting a heat conduction layer or a heat dissipation layer on the battery casing, which can speed up the thermal diffusion on the surface of the battery cell, but still cannot improve the temperature inside the battery cell. The uniformity of temperature distribution cannot solve the problems of local heat accumulation inside the battery; (2) Adding a vapor chamber inside the cell can only improve the uniformity of temperature distribution inside the cell to a certain extent, because it does not directly improve The uniformity of heat production of the heating sheet itself, when the battery has a built-in heating sheet that can quickly heat up, the temperature equalization effect of the soaking plate is not ideal, and it mainly accelerates the heat dissipation of the battery, and cannot make full use of the heat generated by the heating sheet itself. That is, it is impossible to promote the conduction of heat from the parts with high heat generation to the parts with low heat generation, so that the heating sheet itself can not only heat up quickly but also produce heat evenly.
发明内容Contents of the invention
有鉴于此，本申请旨在提供一种电化学装置，以解决现有电芯内置的加热片采用均一导热性绝缘材质封装后，在快速升温时加热片表面温度产热和散热不均匀，从而导致电芯内部温度不均匀的问题。In view of this, the purpose of this application is to provide an electrochemical device to solve the problem of uneven heat generation and heat dissipation on the surface of the heating sheet when the heating sheet is heated rapidly when the heating sheet built in the existing electric core is packaged with a uniform thermal conductivity insulating material, thereby Causes the problem of uneven temperature inside the battery cell.
本申请一种实施方式的技术方案是：一种电化学装置，其包括加热组件，所述加热组件包括加热部以及围绕所述加热部设置的均热部。所述均热部包括互不重叠的第一均热部和第二均热部，所述第一均热部和所述第二均热部的热阻值倒数之比大于或等于1.05，所述第一均热部和所述第二均热部的面积分别大于2cm
2。一种实施方式中，所述第一均热部和所述第二均热部的热阻值倒数之比优选为大于1.2。一种实施方式中，所述第一均热部和第二均热部热阻值倒数之比为大于1.6。一种实施方式中，所述第一均热部和第二均热部热阻值倒数之比为大于1.75。
The technical solution of one embodiment of the present application is: an electrochemical device, which includes a heating assembly, and the heating assembly includes a heating part and a heat equalizing part arranged around the heating part. The heat equalizing portion includes a first heat equalizing portion and a second heat equalizing portion that do not overlap each other, and the ratio of the reciprocal of the thermal resistance of the first heat equalizing portion to the second heat equalizing portion is greater than or equal to 1.05, so The areas of the first heat soaking portion and the second heat soaking portion are respectively greater than 2 cm 2 . In one embodiment, the ratio of the reciprocal of the thermal resistance of the first heat soaking part to the second heat soaking part is preferably greater than 1.2. In one embodiment, the ratio of the reciprocal of the thermal resistance of the first heat soaking part to the second heat soaking part is greater than 1.6. In one embodiment, the ratio of the reciprocal of the thermal resistance of the first heat soaking part to the second heat soaking part is greater than 1.75.
根据电化学装置表面的温度分布特性，对内置的加热组件采用具有不同热传导能力的均热部(绝缘材料)进行封装，在加热组件的加热部产热低温度低的部位采用高热传导能力的均热部(绝缘材料)封装，在产热高温度高的部位采用低热传导能力的均热部(绝缘材料)封装，可以削减产热高的部位沿Z方向(加热部的内部向均热部的表面方向，即加热组件的厚度方向，也即电化学装置的厚度方向)的热传导能力，并且在温差的作用下，会促进一部分热量通过加热部沿X方向(加热组件的长度方向，也即电化学装置的长度方向)和Y方向(加热组件的宽度方向，也即电化学装置的宽度方向)朝温度低的部位传导，从而提高温度低的部位的温度，进而改善电化学装置的温度均匀性。According to the temperature distribution characteristics of the surface of the electrochemical device, the built-in heating components are packaged with heat-spreading parts (insulating materials) with different heat conduction capabilities, and the heat-generating parts of the heating parts with low heat generation and low temperature are packaged with heat-spreading parts with high heat conduction capabilities. Heat part (insulation material) package, use heat soaking part (insulation material) package with low thermal conductivity in the part with high heat generation and high temperature, which can reduce the heat generation part along the Z direction (inside the heating part to the heat soaking part) Surface direction, that is, the thickness direction of the heating component, that is, the thickness direction of the electrochemical device), and under the action of temperature difference, it will promote a part of the heat to pass through the heating part along the X direction (the length direction of the heating component, that is, the electrical The length direction of the chemical device) and the Y direction (the width direction of the heating component, that is, the width direction of the electrochemical device) conduct to the low temperature part, thereby increasing the temperature of the low temperature part, thereby improving the temperature uniformity of the electrochemical device .
一种实施方式中，所述热阻值倒数的计算公式为C＝λS/L，其中，λ为均热部的热传导系数，L为均热部的厚度，S为均热部的面积。In one embodiment, the formula for calculating the reciprocal of the thermal resistance is C=λS/L, where λ is the thermal conductivity coefficient of the soaking portion, L is the thickness of the soaking portion, and S is the area of the soaking portion.
一种实施方式中，所述加热部的电阻率范围为10
-8Ω·m至10
-5Ω·m，所述加热部的厚度为1μm至80μm。所述加热部材料的电阻率不宜过大，否则容易导致局部热量不均的问题；所述加热部材料的电阻率不宜过小，以保证加热部加热效率。加热部的厚度不宜过大，以保证加热部的加热效率，以及电化学装置的能量密度；加热部的厚度不宜过小，以确保加热部具有较高的电子传导能力和载流能力，从而可以保证加热部的加热功能。
In one embodiment, the resistivity of the heating part ranges from 10 -8 Ω·m to 10 -5 Ω·m, and the thickness of the heating part ranges from 1 μm to 80 μm. The resistivity of the material of the heating part should not be too large, otherwise it will easily lead to the problem of uneven local heat; the resistivity of the material of the heating part should not be too small to ensure the heating efficiency of the heating part. The thickness of the heating part should not be too large to ensure the heating efficiency of the heating part and the energy density of the electrochemical device; the thickness of the heating part should not be too small to ensure that the heating part has high electron conductivity and current carrying capacity, so that it can Ensure the heating function of the heating part.
所述均热部的热传导系数范围为0.1W/m·K至100W/m·K，所述均热部的厚度范围为1μm至80μm。均热部的厚度不宜过大，以保证电化学装置的能量密度；均热部的厚度不宜过小，从而保证其具有一定的机械强度和保护作用，可保证加热部不会与电化学装置的极片直接连通，引发失效。The thermal conductivity of the heat soaking portion ranges from 0.1 W/m·K to 100 W/m·K, and the thickness of the heat soaking portion ranges from 1 μm to 80 μm. The thickness of the soaking part should not be too large to ensure the energy density of the electrochemical device; the thickness of the soaking part should not be too small to ensure that it has a certain mechanical strength and protective effect, and can ensure that the heating part will not interfere with the electrochemical device The pole piece is directly connected, causing failure.
一种实施方式中，所述加热部可以具有一定图案。一种实施方式中，所述加热部具有的图案包括方波形图案、回字纹、锯齿形、水波形中的至少一种。In one embodiment, the heating part may have a certain pattern. In one embodiment, the pattern of the heating part includes at least one of a square wave pattern, a zigzag pattern, a zigzag pattern, and a water wave pattern.
一种实施方式中，所述均热部包括第一均热部、第二均热部…和第N均热部，其中N是大于或等于3的整数，第一均热部的热阻值倒数＞第二均热部的热阻值倒数＞…＞第N均热部的热阻值倒数。In one embodiment, the heat soaking part includes a first heat soaking part, a second heat soaking part ... and an Nth heat soaking part, wherein N is an integer greater than or equal to 3, and the thermal resistance of the first heat soaking part The reciprocal>the reciprocal of the thermal resistance of the second heat soaking part>...>the reciprocal of the thermal resistance of the Nth heat soaking part.
一种实施方式中，所述加热部的材质包括金属材料、碳系导电材料、金属氧化物或导电高分子材料中的至少一种。In one embodiment, the material of the heating part includes at least one of metal material, carbon-based conductive material, metal oxide or conductive polymer material.
一种实施方式中，所述金属材料包括镍、钛、铜、金、银、铂、铁、钴、铬、钨、钼、铝、镁、钾、钠、钙、锶、钡、硅、锗、锑、铅、铟、锌或由上述元素构成的组合物中的至少一种。In one embodiment, the metal material includes nickel, titanium, copper, gold, silver, platinum, iron, cobalt, chromium, tungsten, molybdenum, aluminum, magnesium, potassium, sodium, calcium, strontium, barium, silicon, germanium , antimony, lead, indium, zinc, or at least one of a combination of these elements.
一种实施方式中，所述碳系导电材料包括炭黑、石墨、石墨烯、碳纤维、单壁碳纳米管或多壁纳米管中的至少一种。In one embodiment, the carbon-based conductive material includes at least one of carbon black, graphite, graphene, carbon fiber, single-walled carbon nanotubes, or multi-walled nanotubes.
一种实施方式中，所述金属氧化物包括掺铝氧化锌、掺钙铬酸镧、二氧化锡、掺氟二氧化锡、掺锑二氧化锡、氧化铟锡、掺银氧化铟锡或掺银合金氧化铟锡中的至少一种。In one embodiment, the metal oxide includes aluminum-doped zinc oxide, calcium-doped lanthanum chromate, tin dioxide, fluorine-doped tin dioxide, antimony-doped tin dioxide, indium tin oxide, silver-doped indium tin oxide, or At least one of silver alloy indium tin oxide.
一种实施方式中，所述导电高分子材料包括聚乙炔、聚吡咯、聚噻吩、聚对苯、聚苯乙炔、聚苯胺或其掺杂高分子材料中的至少一种，所述掺杂高分子材料中的掺杂剂包括氯、碘、溴、氯化碘、溴化碘、氟化碘、五氟化磷、氢氟酸、盐酸、硝酸、硫酸、高氯酸、五氟化钼、五氟化钨、四氯化钛、四氯化锆、氯化铁或四碘化锡中的至少一种。In one embodiment, the conductive polymer material includes at least one of polyacetylene, polypyrrole, polythiophene, polyparaphenylene, polyphenylene vinylene, polyaniline or its doped polymer material, and the doped high Dopants in molecular materials include chlorine, iodine, bromine, iodine chloride, iodine bromide, iodine fluoride, phosphorus pentafluoride, hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, molybdenum pentafluoride, At least one of tungsten pentafluoride, titanium tetrachloride, zirconium tetrachloride, ferric chloride or tin tetraiodide.
一种实施方式中，所述均热部的材质包括导热硅脂、硅胶、导热泥、灌封胶、ABS塑料、软质和硬质PVC、石蜡、石棉、硬木、软木、UP树脂、有机玻璃、聚碳酸酯、尼龙、聚乙烯、聚丙烯、异丁烯、聚酰胺、聚酰亚胺、聚硫胶、聚酯树脂、聚亚胺脂树脂、氯丁橡胶、聚酯马海毛、人造橡胶泡沫、聚氨酯、环氧树脂、聚苯硫醚塑料、聚酰胺、石墨、三氧化二铝、氧化镁、氧化锌或氧化镍中的至少一种。In one embodiment, the material of the soaking part includes thermally conductive silicone grease, silica gel, thermally conductive putty, potting glue, ABS plastic, soft and hard PVC, paraffin, asbestos, hardwood, cork, UP resin, organic glass , polycarbonate, nylon, polyethylene, polypropylene, isobutylene, polyamide, polyimide, polysulfide, polyester resin, polyurethane resin, neoprene, polyester mohair, elastomeric foam, polyurethane , epoxy resin, polyphenylene sulfide plastic, polyamide, graphite, aluminum oxide, magnesium oxide, zinc oxide or nickel oxide.
一种实施方式中，所述加热组件包括第一极耳和第二极耳，所述第一极耳和 所述第二极耳均设置于所述加热部上，且均与所述加热部电连接。In one embodiment, the heating assembly includes a first tab and a second tab, the first tab and the second tab are both arranged on the heating part, and are connected to the heating part electrical connection.
一种实施方式中，所述电化学装置还包括正极极片和负极极片，所述加热组件与所述正极极片或所述负极极片相接触。In one embodiment, the electrochemical device further includes a positive pole piece and a negative pole piece, and the heating assembly is in contact with the positive pole piece or the negative pole piece.
本申请还提供一种二次电池，所述二次电池包括如上所述的电化学装置、温度感应装置、以及与所述温度感应装置和所述加热组件相连接的控制***，所述控制***可根据所述温度感应装置检测到的温度，控制加热组件所处电路处于导通或断开状态。The present application also provides a secondary battery, which includes the above-mentioned electrochemical device, a temperature sensing device, and a control system connected with the temperature sensing device and the heating assembly, the control system According to the temperature detected by the temperature sensing device, the circuit where the heating component is located can be controlled to be on or off.
一种实施方式中，所述控制***可根据所述温度感应装置检测到的温度，以及设定的目标温度T，控制加热组件所处电路处于导通或断开状态。In one embodiment, the control system can control the circuit where the heating component is located to be on or off according to the temperature detected by the temperature sensing device and the set target temperature T.
一种实施方式中，控制***读取所述温度感应装置检测到的温度，当所述检测温度低于所述目标温度T时，所述电路处于导通状态，电流通过所述加热组件，加热组件实现对电化学装置的加热功能。当所述温度感应装置检测到的温度达到加热目标温度T后，所述控制***控制所述电路断开，加热组件停止加热。In one embodiment, the control system reads the temperature detected by the temperature sensing device, and when the detected temperature is lower than the target temperature T, the circuit is in a conducting state, and the current passes through the heating component to heat The component realizes the heating function of the electrochemical device. When the temperature detected by the temperature sensing device reaches the heating target temperature T, the control system controls the circuit to be disconnected, and the heating component stops heating.
一种实施方式中，控制***读取电化学装置的温度，当所述电化学装置的温度大于或等于T时，所述电路处于断开状态。In one embodiment, the control system reads the temperature of the electrochemical device, and when the temperature of the electrochemical device is greater than or equal to T, the circuit is in an open state.
一种实施方式中，所述电路处于导通状态时，加热组件由电化学装置或外部电源供电，加热组件处于工作模式；所述电路处于断开状态时，加热组件不产生热量。In one embodiment, when the circuit is on, the heating component is powered by an electrochemical device or an external power supply, and the heating component is in a working mode; when the circuit is off, the heating component does not generate heat.
本申请提供的电化学装置，根据其表面的温度分布特性，对内置的加热组件采用具有不同热传导能力的绝缘材料进行封装。在加热组件的加热部产热低温度低的部位采用高热传导能力的绝缘材料封装，在产热高温度高的部位采用低热传导能力的材质封装，可以削减产热高的部位沿Z方向(加热部的内部向均热部的表面方向，即加热组件的厚度方向，也即电化学装置的厚度方向)的热传导能力，并且在温差的作用下，会促进一部分热量通过加热部沿X方向(加热组件的长度方向，也即电化学装置的长度方向)和Y方向(加热组件的宽度方向，也即电化学装置的宽度方向)朝温度低的部位传导，从而提高温度低的部位的温度。本申请提供的电化学装置可充分利用加热部产生的热量，有效降低加热部表面的温度差异性，实现加热组件的均匀产热，并最终实现在电化学装置快速升温的同时改善电化学装置的温度均匀性。In the electrochemical device provided by the present application, the built-in heating components are packaged with insulating materials with different thermal conductivity according to the temperature distribution characteristics of the surface. The parts with low heat generation and low temperature in the heating part of the heating element are packaged with insulating material with high thermal conductivity, and the parts with high heat generation and high temperature are packaged with materials with low heat conductivity, which can reduce the position of high heat generation along the Z direction (heating part to the surface of the heat soaking part, that is, the thickness direction of the heating assembly, that is, the thickness direction of the electrochemical device), and under the action of the temperature difference, a part of the heat will be promoted to pass through the heating part along the X direction (heating The length direction of the assembly (that is, the length direction of the electrochemical device) and the Y direction (the width direction of the heating assembly, that is, the width direction of the electrochemical device) are conducted to the low temperature part, thereby increasing the temperature of the low temperature part. The electrochemical device provided by this application can make full use of the heat generated by the heating part, effectively reduce the temperature difference on the surface of the heating part, realize the uniform heat generation of the heating component, and finally realize the rapid heating of the electrochemical device while improving the performance of the electrochemical device. temperature uniformity.
下面结合附图和具体实施方式对本申请作进一步详细的说明。The present application will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.
图1为现有技术中内置加热片加热时电芯表面的温度分布图。Fig. 1 is a diagram of the temperature distribution on the surface of the battery cell when the built-in heating sheet is heated in the prior art.
图2为本申请一种或几种实施方式提供的电化学装置的示意图。Fig. 2 is a schematic diagram of an electrochemical device provided by one or several embodiments of the present application.
图3为本申请一种或几种实施方式提供的加热组件的示意图。Fig. 3 is a schematic diagram of a heating assembly provided in one or several embodiments of the present application.
图4为本申请一种或几种实施方式提供的加热组件的示意图。Fig. 4 is a schematic diagram of a heating assembly provided in one or several embodiments of the present application.
图5为本申请一种或几种实施方式提供的加热部的示意图。Fig. 5 is a schematic diagram of a heating part provided in one or several embodiments of the present application.
主要元件符号说明：Description of main component symbols:
电化学装置 100 Electrochemical device 100
极耳 200 Ears 200
加热组件 10 Heating element 10
加热部 11 Heating Department 11
均热部 12soaking part 12
第一极耳 13 First tab 13
第二极耳 14 Second tab 14
第一均热部 121The first soaking part 121
第二均热部 122The second soaking part 122
第三均热部 123The third soaking part 123
长度方向 XLength direction X
宽度方向 YWidth direction Y
厚度方向 ZThickness direction Z
如下具体实施方式将结合上述附图进一步说明本申请实施例。The following specific implementation manner will further describe the embodiments of the present application in conjunction with the above-mentioned drawings.
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请实施例的技术领域的技术人员通常理解的含义相同。本文中所使用的术语只是为了描述具体的实施方式的目的，不是旨在于限制本申请实施例。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field of the embodiments of this application. The terminology used herein is only for the purpose of describing specific implementation manners, and is not intended to limit the embodiments of the present application.
空间相关术语，比如“上”等可在本文用于方便描述，以描述如图中阐释的一个要素或特征与另一要素(多个要素)或特征(多个特征)的关系。应理解，除了图中描述的方向之外，空间相关术语旨在包括设备或装置在使用或操作中的不同方向。例如，如果将图中的设备翻转，则描述为在其他要素或特征“上方”或“上”的要素将定向在其他要素或特征的“下方”或“下面”。因此，示例性术 语“上”可包括上面和下面的方向。Spatially relative terms such as "on" and the like may be used herein for convenience of description to describe the relationship of one element or feature to another element(s) or feature(s) as illustrated in the figures. It will be understood that spatially relative terms are intended to encompass different orientations of the device or device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as "above" or "on" other elements or features would then be oriented "below" or "beneath" the other elements or features. Thus, the exemplary term "on" can encompass both an orientation of above and below.
应理解，尽管术语第一、第二、第三等可在本文用于描述各种要素、组分、区域、层和/或部分，但是这些要素、组分、区域、层和/或部分不应受这些术语的限制。这些术语用于区分一个要素、组分、区域、层或部分与另一要素、组分、区域、层或部分。因此，下面讨论的第一要素、组分、区域、层或部分可称为第二要素、组分、区域、层或部分，而不背离示例性实施方式的教导。It should be understood that although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections do not shall be limited by these terms. These terms are used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the example embodiments.
本申请中，定义加热组件的厚度方向(电化学装置的厚度方向)为Z方向，定义加热组件的长度方向(电化学装置的长度方向)为X方向，定义加热组件的宽度方向(电化学装置的宽度方向)为Y方向。可以理解，当电化学装置或加热组件呈不规则形状时，加热组件的均热部的具体设置随着电化学装置的温度分布而变化，变化的原则是：温度较低的部位采用热阻值倒数较大的绝缘材料(均热部)对加热部进行封装，在温度较高的部位采用热阻值倒数小的绝缘材料(均热部)对加热部进行封装。In this application, the thickness direction of the heating assembly (the thickness direction of the electrochemical device) is defined as the Z direction, the longitudinal direction of the heating assembly (the length direction of the electrochemical device) is defined as the X direction, and the width direction of the heating assembly (the electrochemical device) is defined as the X direction. The width direction) is the Y direction. It can be understood that when the electrochemical device or the heating assembly is irregular in shape, the specific setting of the soaking part of the heating assembly changes with the temperature distribution of the electrochemical device. The insulating material (soaking part) with a larger reciprocal value is used to encapsulate the heating part, and the insulating material (soaking part) with a smaller reciprocal value of thermal resistance is used to encapsulate the heating part at the part with a higher temperature.
下面对本申请的一些实施方式作详细说明。在不冲突的情况下，下述的实施例及实施例中的特征可以相互组合。Some implementations of the present application will be described in detail below. In the case of no conflict, the following embodiments and features in the embodiments can be combined with each other.
请参阅图2，本申请提供一种电化学装置100，所述电化学装置100包括加热组件10。请参阅图3，所述加热组件10包括加热部11以及围绕所述加热部11设置的均热部12，即加热部11的表面均被所述均热部12所覆盖。所述均热部12包括互不重叠的第一均热部121和第二均热部122，所述第一均热部121和所述第二均热部122的热阻值倒数之比大于或等于1.05，所述第一均热部121和所述第二均热部122的面积分别大于2cm
2。一些实施方式中，所述第一均热部121和所述第二均热部122的热阻值倒数之比优选为大于1.2。一些实施方式中，所述第一均热部121和第二均热部122热阻值倒数之比为大于1.6。一些实施方式中，所述第一均热部121和第二均热部122热阻值倒数之比为大于1.75。
Referring to FIG. 2 , the present application provides an electrochemical device 100 , and the electrochemical device 100 includes a heating component 10 . Referring to FIG. 3 , the heating assembly 10 includes a heating part 11 and a heat soaking part 12 disposed around the heating part 11 , that is, the surface of the heating part 11 is covered by the heat soaking part 12 . The heat equalizing portion 12 includes a first heat equalizing portion 121 and a second heat equalizing portion 122 that do not overlap each other, and the ratio of the reciprocal of the thermal resistance of the first heat equalizing portion 121 to the second heat equalizing portion 122 is greater than Or equal to 1.05, the areas of the first heat equalizing portion 121 and the second heat equalizing portion 122 are respectively greater than 2 cm 2 . In some implementations, the ratio of the reciprocal of the thermal resistance of the first heat equalizing portion 121 and the second heat equalizing portion 122 is preferably greater than 1.2. In some embodiments, the ratio of the reciprocal of the thermal resistance of the first heat-spreading portion 121 and the second heat-spreading portion 122 is greater than 1.6. In some embodiments, the ratio of the reciprocal of the thermal resistance of the first heat-spreading portion 121 and the second heat-spreading portion 122 is greater than 1.75.
由图1可知，沿X方向，电化学装置的温度从下到上(图中极耳200所在的位置为上方)递减。本申请中，沿X方向，在加热部11的温度较低的部位采用热阻值倒数较大的第一均热部121对加热部11封装，在加热部11的温度较高的部位采用热阻值倒数小的第二均热部122对加热部11封装，可以削减加热部11上温度较高的部位沿Z方向的热传导能力，并且在温差的作用下，会促进一部分热量沿X方向和Y方向朝温度较低的部位传导，从而提高温度较低的部位的温度。It can be seen from FIG. 1 that along the X direction, the temperature of the electrochemical device decreases gradually from bottom to top (the position where the tab 200 is located is the top). In this application, along the X-direction, the heating part 11 is packaged with the first heat soaking part 121 with a relatively large reciprocal of the thermal resistance value at the lower temperature part of the heating part 11, and the thermal The second heat soaking part 122 with the smallest reciprocal resistance is packaged on the heating part 11, which can reduce the heat conduction ability of the part with a higher temperature on the heating part 11 along the Z direction, and under the action of the temperature difference, a part of the heat will be promoted along the X direction and The Y-direction conducts toward the lower temperature area, thereby increasing the temperature of the lower temperature area.
一些实施方式中，所述热阻值倒数的计算公式为C＝λS/L，其中，λ为均热部的热传导系数，L为均热部的厚度，S为均热部的面积。本申请中，所述均热部的面积为均热部沿厚度方向Z方向的投影的面积，均热部的厚度L通过游标卡尺测量，单个区域(例如，直径25mm)测量多个点(4个以上)的厚度并取平均值。所述热传导系数通过以下方法测量：采用导热系数仪(如Unitherm
TM2022)进行测量，将样品放置在两个表面抛光的金属板(即上板和下板)之间，上板和下板分别控制在不同的温度，下板的下表面是定标过的热流传感器；当样品的上表面与下表面之间保持一定的温度差达到热平衡时就产生从上至下经过样品的纵向热流；通过测量样品上下表面的温差(样品上下表面的温差用置于样品上下两端的高导热金属的表面处的温度传感器测量)、热流传感器的读数以及已知的样品的厚度，就可以计算出热传导系数。
In some embodiments, the formula for calculating the reciprocal of the thermal resistance is C=λS/L, where λ is the thermal conductivity coefficient of the soaking portion, L is the thickness of the soaking portion, and S is the area of the soaking portion. In the present application, the area of the soaking portion is the projected area of the soaking portion along the thickness direction Z direction, the thickness L of the soaking portion is measured by a vernier caliper, and a single area (for example, a diameter of 25mm) measures multiple points (4 above) and take the average value. The thermal conductivity is measured by the following method: a thermal conductivity meter (such as Unitherm TM 2022) is used for measurement, and the sample is placed between two surface-polished metal plates (ie, an upper plate and a lower plate), and the upper plate and the lower plate are respectively Controlled at different temperatures, the lower surface of the lower plate is a calibrated heat flow sensor; when a certain temperature difference is maintained between the upper surface and the lower surface of the sample to achieve thermal equilibrium, a longitudinal heat flow passing through the sample from top to bottom is generated; through The thermal conductivity coefficient can be calculated by measuring the temperature difference between the upper and lower surfaces of the sample (the temperature difference between the upper and lower surfaces of the sample is measured by a temperature sensor placed on the surface of the high thermal conductivity metal at the upper and lower ends of the sample), the reading of the heat flow sensor and the known thickness of the sample.
一些实施方式中，所述均热部12包括第一均热部121、第二均热部122…和第N均热部，其中N是大于或等于3的整数，第一均热部121的热阻值倒数＞第二均热部122的热阻值倒数＞…＞第N均热部的热阻值倒数。如图4所示，所述均热部12包括第一均热部121、第二均热部122和第三均热部123，第一均热部121的热阻值倒数＞第二均热部122的热阻值倒数＞第三均热部123的热阻值倒数。In some embodiments, the heat equalizing portion 12 includes a first heat equalizing portion 121, a second heat equalizing portion 122... and an Nth heat equalizing portion, wherein N is an integer greater than or equal to 3, and the first heat equalizing portion 121 The reciprocal of the thermal resistance value>the reciprocal of the thermal resistance value of the second heat soaking part 122>...>the reciprocal of the thermal resistance value of the Nth heat soaking part. As shown in FIG. 4 , the heat soaking part 12 includes a first heat soaking part 121 , a second heat soaking part 122 and a third heat soaking part 123 , and the reciprocal of the thermal resistance of the first heat soaking part 121 > the second heat soaking part The reciprocal of the thermal resistance of the part 122 > the reciprocal of the thermal resistance of the third heat equalizing part 123 .
进一步地，所述第一均热部121的热传导能力大于所述第二均热部122的热传导能力，所述第二均热部122的热传导能力大于所述第三均热部123的热传导能力，第N-1均热部的热传导能力大于所述第N均热部的热传导能力，所述热传导能力指的是单位面积的均热部的热阻值倒数。Further, the heat conduction capacity of the first heat equalization part 121 is greater than the heat conduction capacity of the second heat equalization part 122 , and the heat conduction capacity of the second heat equalization part 122 is greater than the heat conduction capacity of the third heat equalization part 123 , the heat conduction capability of the N-1th heat soaking part is greater than the heat conduction capability of the Nth heat soaking part, and the heat conduction capability refers to the reciprocal of the thermal resistance value of the heat soaking part per unit area.
进一步地，所述第一均热部121、第二均热部122、第三均热部123，可以根据加热部及电芯工作时的温度分布情况，进行均热部区域的划分及材料的选择。Further, the first heat soaking part 121, the second heat soaking part 122, and the third heat soaking part 123 can divide the area of the heat soaking part and the material of the heat soaking part according to the temperature distribution of the heating part and the electric core during operation. choose.
一些实施方式中，所述加热部11的电阻率范围为10
-8Ω·m至10
-5Ω·m，所述加热部11的厚度为1μm至80μm。加热部11的厚度不宜过大，以保证加热部11的加热效率，以及电化学装置100的能量密度；加热部11的厚度不宜过小，以确保加热部11具有较高的电子传导能力和载流能力，从而可以保证加热部11的加热功能。
In some embodiments, the resistivity of the heating part 11 ranges from 10 -8 Ω·m to 10 -5 Ω·m, and the thickness of the heating part 11 is 1 μm to 80 μm. The thickness of the heating part 11 should not be too large to ensure the heating efficiency of the heating part 11 and the energy density of the electrochemical device 100; the thickness of the heating part 11 should not be too small to ensure that the heating part 11 has a higher electron conductivity and load capacity. flow capacity, so that the heating function of the heating part 11 can be ensured.
一些实施方式中，所述加热部11可以具有一定图案。一些实施方式中，所述加热部具有方波形图案。一些实施方式中，所述加热部也可具有回字纹、锯齿 形、水波形等其他图案。可以理解，加热部的形状、材料的宽度等均可根据电芯的形状及温度分布进行设计，从而保证加热部11对电化学装置100的充分加热。In some embodiments, the heating part 11 may have a certain pattern. In some embodiments, the heating portion has a square wave pattern. In some embodiments, the heating part may also have other patterns such as zigzagging, zigzag, and water waves. It can be understood that the shape of the heating part, the width of the material, etc. can be designed according to the shape of the cell and the temperature distribution, so as to ensure sufficient heating of the electrochemical device 100 by the heating part 11 .
一些实施方式中，所述均热部12的热传导系数范围为0.1W/m·K至100W/m·K，所述均热部12的厚度范围为1μm至80μm。均热部12的厚度不宜过大，以保证电化学装置100的能量密度；均热部12的厚度不宜过小，从而保证其具有一定的机械强度和保护作用，可保证加热部11不会与电化学装置100的极片直接连通，引发失效。In some embodiments, the thermal conductivity of the heat soaking portion 12 ranges from 0.1 W/m·K to 100 W/m·K, and the thickness of the heat soaking portion 12 ranges from 1 μm to 80 μm. The thickness of the soaking part 12 should not be too large, so as to ensure the energy density of the electrochemical device 100; The pole pieces of the electrochemical device 100 are directly connected, causing failure.
一些实施方式中，所述加热部11的材质包括金属材料、碳系导电材料、金属氧化物或导电高分子材料中的至少一种。In some embodiments, the material of the heating part 11 includes at least one of metal material, carbon-based conductive material, metal oxide or conductive polymer material.
进一步地，所述金属材料包括镍(Ni)、钛(Ti)、铜(Cu)、金(Au)、银(Ag)、铂(Pt)、铁(Fe)、钴(Co)、铬(Cr)、钨(W)、钼(Mo)、铝(Al)、镁(Mg)、钾(K)、钠(Na)、钙(Ca)、锶(Sr)、钡(Ba)、硅(Si)、锗(Ge)、锑(Sb)、铅(Pb)、铟(In)、锌(Zn)及其组合物(合金)中的至少一种。Further, the metal material includes nickel (Ni), titanium (Ti), copper (Cu), gold (Au), silver (Ag), platinum (Pt), iron (Fe), cobalt (Co), chromium ( Cr), tungsten (W), molybdenum (Mo), aluminum (Al), magnesium (Mg), potassium (K), sodium (Na), calcium (Ca), strontium (Sr), barium (Ba), silicon ( At least one of Si), germanium (Ge), antimony (Sb), lead (Pb), indium (In), zinc (Zn) and combinations (alloys) thereof.
进一步地，所述碳系导电材料包括炭黑、石墨、石墨烯、碳纤维、单壁碳纳米管或多壁纳米管中的至少一种。Further, the carbon-based conductive material includes at least one of carbon black, graphite, graphene, carbon fiber, single-walled carbon nanotubes or multi-walled nanotubes.
进一步地，所述金属氧化物包括掺铝氧化锌、掺钙铬酸镧、二氧化锡、掺氟二氧化锡、掺锑二氧化锡、氧化铟锡、掺银氧化铟锡或掺银合金氧化铟锡中的至少一种。Further, the metal oxide includes aluminum-doped zinc oxide, calcium-doped lanthanum chromate, tin dioxide, fluorine-doped tin dioxide, antimony-doped tin dioxide, indium tin oxide, silver-doped indium tin oxide or silver-doped alloy oxide at least one of indium tin.
进一步地，所述导电高分子材料包括聚乙炔、聚吡咯、聚噻吩、聚对苯、聚苯乙炔、聚苯胺或其掺杂高分子材料中的至少一种，所述掺杂高分子材料中的掺杂剂包括氯、碘、溴、氯化碘、溴化碘、氟化碘、五氟化磷、氢氟酸、盐酸、硝酸、硫酸、高氯酸、五氟化钼、五氟化钨、四氯化钛、四氯化锆、氯化铁或四碘化锡中的至少一种。Further, the conductive polymer material includes at least one of polyacetylene, polypyrrole, polythiophene, polyparaphenylene, polyphenylene vinylene, polyaniline or its doped polymer material, and the doped polymer material Dopants include chlorine, iodine, bromine, iodine chloride, iodine bromide, iodine fluoride, phosphorus pentafluoride, hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, molybdenum pentafluoride, pentafluoride At least one of tungsten, titanium tetrachloride, zirconium tetrachloride, ferric chloride or tin tetraiodide.
一些实施方式中，所述均热部12的材质为具有热传导能力的绝缘材料，包括导热硅脂、硅胶、导热泥、灌封胶、ABS塑料、软质和硬质PVC(聚氯乙烯)、石蜡、石棉、硬木、软木、UP树脂(不饱和聚酯)、有机玻璃(PMMA)、聚碳酸酯、尼龙、聚乙烯、聚丙烯(PP)、异丁烯、聚酰胺(PA)、聚酰亚胺(PI)、聚硫胶、聚酯树脂、聚亚胺脂树脂、氯丁橡胶(PCP)、聚酯马海毛、人造橡胶泡沫、聚氨酯、环氧树脂、聚苯硫醚塑料、聚酰胺、石墨、三氧化二铝(Al
2O
3)、氧化镁(MgO)、氧化锌(ZnO)或氧化镍(NiO)中的至少一种。
In some embodiments, the material of the heat equalizing part 12 is an insulating material with thermal conductivity, including thermal conductive silicone grease, silica gel, thermal conductive paste, potting glue, ABS plastic, soft and hard PVC (polyvinyl chloride), Paraffin, asbestos, hardwood, cork, UP resin (unsaturated polyester), plexiglass (PMMA), polycarbonate, nylon, polyethylene, polypropylene (PP), isobutylene, polyamide (PA), polyimide (PI), polysulfide, polyester resin, polyurethane resin, neoprene (PCP), polyester mohair, elastomeric foam, polyurethane, epoxy resin, polyphenylene sulfide plastic, polyamide, graphite, At least one of aluminum oxide (Al 2 O 3 ), magnesium oxide (MgO), zinc oxide (ZnO) or nickel oxide (NiO).
请参阅图3和图4，所述加热组件10包括第一极耳13和第二极耳14。请参阅图5，所述第一极耳13和所述第二极耳14均设置于所述加热部11上，且均与所述加热部11电连接。Referring to FIG. 3 and FIG. 4 , the heating assembly 10 includes a first tab 13 and a second tab 14 . Referring to FIG. 5 , both the first tab 13 and the second tab 14 are disposed on the heating portion 11 and are electrically connected to the heating portion 11 .
一些实施方式中，所述电化学装置还包括正极极片和负极极片，所述加热组件与所述正极极片或所述负极极片中的至少一者相接触。In some embodiments, the electrochemical device further includes a positive pole piece and a negative pole piece, and the heating assembly is in contact with at least one of the positive pole piece or the negative pole piece.
以下将结合具体实施例对本申请作进一步详细的说明。The present application will be described in further detail below in conjunction with specific embodiments.
实施例1Example 1
(1)加热组件的制备(1) Preparation of heating components
取一片厚度为20μm且表面光滑的铜片，在其表面通过激光切割出回路，所述回路按照附图5所示方波形图案进行加工，得到加热部11。在铜片左右两侧各焊接一个镍极耳，即第一极耳13和第二极耳14。如图4所示，第一均热部121采用高密度聚乙烯(热传导系数：0.4W/m·K-0.5W/m·K)对铜片进行热封，第二均热部122采用低密度聚乙烯(热传导系数：0.2-0.3W/m·K)进行热封，第一均热部121和第二均热部122的厚度相同，皆为10μm。第一均热部121和第二均热部122围绕所述铜片，即得到加热组件。Take a piece of copper sheet with a thickness of 20 μm and a smooth surface, cut a circuit on its surface by laser, and process the circuit according to the square wave pattern shown in FIG. 5 to obtain the heating part 11 . A nickel tab is welded on the left and right sides of the copper sheet, that is, the first tab 13 and the second tab 14 . As shown in Figure 4, the first heat soaking part 121 uses high density polyethylene (thermal conductivity: 0.4W/m·K-0.5W/m·K) to heat seal the copper sheet, and the second heat soaking part 122 uses low Density polyethylene (thermal conductivity: 0.2-0.3 W/m·K) is heat-sealed, and the thickness of the first heat soaking part 121 and the second heat soaking part 122 are the same, both being 10 μm. The first heat equalizing portion 121 and the second heat equalizing portion 122 surround the copper sheet, ie a heating assembly is obtained.
(2)正极极片的制备(2) Preparation of positive pole piece
将正极活性材料钴酸锂(LiCoO
2)、导电炭黑(Super P)、聚偏二氟乙烯(PVDF)按照重量比97.5:1.0:1.5进行混合，加入N-甲基吡咯烷酮(NMP)作为溶剂，调配成为固含量为0.75的浆料，并搅拌均匀。将浆料均匀涂覆在Al集流体上，极片上正极有效物质的重量为180g/m
2。90℃条件下烘干，即已完成正极极片的单面涂布，再以同样的方法完成另一面的涂布。完成涂布后，将极片的正极有效物质层冷压至4.0g/cm
3的压实密度，随后进行极耳焊接和贴胶纸等辅助工艺，即完成了双面涂布的正极极片的全部制备流程。
Mix the positive electrode active material lithium cobaltate (LiCoO 2 ), conductive carbon black (Super P), and polyvinylidene fluoride (PVDF) in a weight ratio of 97.5:1.0:1.5, and add N-methylpyrrolidone (NMP) as a solvent , prepared into a slurry with a solid content of 0.75, and stirred evenly. The slurry was uniformly coated on the Al current collector, and the weight of the positive electrode active material on the pole sheet was 180 g/m 2 . Dry at 90°C, that is, the coating on one side of the positive pole piece has been completed, and then the coating on the other side is completed in the same way. After the coating is completed, the positive electrode active material layer of the pole piece is cold-pressed to a compaction density of 4.0g/cm 3 , followed by auxiliary processes such as tab welding and adhesive paper, that is, the double-sided coated positive pole piece is completed the entire preparation process.
(3)负极极片的制备(3) Preparation of negative electrode sheet
将负极活性材料石墨(Graphite)、导电炭黑(Super P)、丁苯橡胶(SBR)按照重量比96:1.5:2.5进行混合，加入去离子水(H
2O)作为溶剂，调配成为固含量为0.7的浆料，并搅拌均匀。将浆料均匀涂覆在Cu集流体上，极片上负极有效物质的重量为95g/m
2。110℃条件下烘干，即已完成极片负极极片的单面涂布，再以同样的方法完成另一面的涂布。完成涂布后，将极片的负极有效物质层冷压至1.7g/cm
3的压实密度。随后进行极耳焊接和贴胶纸等辅助工艺，即完成了双面涂布的负极极片的全部制备流程。
Mix negative electrode active material graphite (Graphite), conductive carbon black (Super P), and styrene-butadiene rubber (SBR) in a weight ratio of 96:1.5:2.5, add deionized water (H 2 O) as a solvent, and prepare a solid content 0.7 slurry, and stir well. The slurry was evenly coated on the Cu current collector, and the weight of the negative electrode active material on the pole piece was 95g/m 2 . Dry at 110°C, that is, the coating on one side of the negative pole piece has been completed, and then the coating on the other side is completed in the same way. After the coating is completed, the negative electrode active material layer of the pole sheet is cold-pressed to a compacted density of 1.7 g/cm 3 . Subsequent auxiliary processes such as tab welding and sticking paper are carried out, that is, the entire preparation process of the double-sided coated negative electrode sheet is completed.
(4)电解液的制备(4) Preparation of electrolyte
在干燥氩气气氛中，首先将有机溶剂碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)和碳酸二乙酯(DEC)以质量比EC:EMC:DEC＝30:50:20混合，然后向有机溶剂中加入锂盐六氟磷酸锂(LiPF
6)溶解并混合均匀，得到锂盐浓度为1.15M的电解液。
In a dry argon atmosphere, at first organic solvent ethylene carbonate (EC), ethyl methyl carbonate (EMC) and diethyl carbonate (DEC) are mixed with mass ratio EC:EMC:DEC=30:50:20, then Add lithium salt lithium hexafluorophosphate (LiPF 6 ) into the organic solvent to dissolve and mix evenly to obtain an electrolyte solution with a lithium salt concentration of 1.15M.
(5)电化学装置的制备(5) Preparation of electrochemical device
选用厚度15μm的聚乙烯(PE)作为隔离膜，将制备好的正极极片、加热组件、隔离膜、负极极片按照顺序叠好并卷绕成电芯，所述加热组件位于电化学装置的卷绕中心，即电芯的卷绕头部。经过顶封和侧封，然后对电芯进行注液，对注液完成的电芯进行化成(0.02C恒流充电到3.3V，再以0.1C恒流充电到3.6V)，最终得到电化学装置。Polyethylene (PE) with a thickness of 15 μm was selected as the separator, and the prepared positive electrode sheet, heating assembly, separator, and negative electrode sheet were stacked in order and wound into a battery core. The heating assembly was located in the electrochemical device. The winding center is the winding head of the battery core. After top sealing and side sealing, the cell is then injected with liquid, and the cell after liquid injection is formed (0.02C constant current charging to 3.3V, and then 0.1C constant current charging to 3.6V), and finally the electrochemical cell is obtained. device.
(6)表面温差测量(6) Surface temperature difference measurement
在环境温度25℃下，外接电源对加热组件10的第一极耳13和第二极耳14施加一定电流启动加热，加热功率为15W时，加热1min，或，加热功率为8W时，加热2min。在敞开体系、室温条件下，采集电化学装置表面的温度分布情况。温度分布情况可采用两种方法测量：第一种是直接接触法进行逐点的温度测量，如热电偶，然后再通过统计方法得到需要的温度场分布信息；另一种方法是采用红外热成像仪进行测量，进而得出电化学装置表面的最大温差。At an ambient temperature of 25°C, an external power supply applies a certain current to the first lug 13 and the second lug 14 of the heating assembly 10 to start heating. When the heating power is 15W, heat for 1min, or when the heating power is 8W, heat for 2min. . Under the condition of open system and room temperature, the temperature distribution on the surface of the electrochemical device is collected. The temperature distribution can be measured by two methods: the first is direct contact method for point-by-point temperature measurement, such as thermocouples, and then obtain the required temperature field distribution information through statistical methods; the other method is to use infrared thermal imaging The instrument is used to measure the maximum temperature difference on the surface of the electrochemical device.
实施例2Example 2
与实施例1的区别在于：步骤(1)中，第一均热部121采用低密度聚乙烯(热传导系数：0.2-0.3W/m·K)，第二均热部122采用低密度硅胶(热传导系数：0.12W/m·K)。The difference from Example 1 is that in step (1), the first soaking part 121 is made of low-density polyethylene (thermal conductivity: 0.2-0.3 W/m K), and the second soaking part 122 is made of low-density silica gel ( Thermal conductivity: 0.12W/m·K).
实施例3Example 3
与实施例1的区别在于：步骤(1)中，第二均热部的厚度为20μm。The difference from Example 1 is that in step (1), the thickness of the second soaking portion is 20 μm.
对比例1Comparative example 1
与实施例1的区别在于：步骤(1)中，采用厚度为10μm的高密度聚乙烯(热传导系数：0.4-0.5W/m·K)对铜片(加热部11)进行热封。The difference from Example 1 is that in step (1), the copper sheet (heating part 11 ) is heat-sealed with high-density polyethylene (thermal conductivity: 0.4-0.5 W/m·K) with a thickness of 10 μm.
对比例2Comparative example 2
与实施例1的区别在于：步骤(1)中，采用厚度为10μm的低密度硅胶(热传导系数：0.12W/m·K)对铜片(加热部11)进行热封。The difference from Example 1 is that in step (1), the copper sheet (heating part 11 ) is heat-sealed with low-density silica gel (thermal conductivity: 0.12 W/m·K) with a thickness of 10 μm.
上述实施例1-3与对比例1-2的各参数设置及测试结果见表1。The parameter settings and test results of the above-mentioned Examples 1-3 and Comparative Examples 1-2 are shown in Table 1.
表1Table 1
实施例4Example 4
与实施例1的区别在于：如图5所示，步骤(1)中，均热部12包括三个封装区域，即第一均热部121、第二均热部122和第三均热部123。第一均热部121采用高密度聚乙烯(热传导系数：0.4-0.5W/m·K)，第二均热部122采用聚酰亚胺(PI)(热传导系数：0.3-0.4W/m·K)，第三均热部123采用低密度聚乙烯(热传导系数：0.2-0.3W/m·K)，三个封装区域的厚度相同，皆为10μm。The difference from Embodiment 1 is that: as shown in Figure 5, in step (1), the heat soaking part 12 includes three packaging areas, namely the first heat soaking part 121, the second heat soaking part 122 and the third heat soaking part 123. The first heat soaking part 121 adopts high-density polyethylene (thermal conductivity: 0.4-0.5W/m K), and the second heat soaking part 122 adopts polyimide (PI) (thermal conductivity: 0.3-0.4W/m K). K), the third heat equalization part 123 is made of low-density polyethylene (thermal conductivity: 0.2-0.3 W/m·K), and the thickness of the three packaging regions is the same, all of which are 10 μm.
实施例5Example 5
与实施例4的区别在于：步骤(1)中，第一均热部121的封装材质为硅胶(热传导系数：0.35W/m·K)，第二均热部122的封装材质为低密度聚乙烯(热传导系数：0.2-0.3W/m·K)，第三均热部123的封装材质为低密度硅胶(热传导系数：0.12W/m·K)。The difference from Embodiment 4 is that in step (1), the packaging material of the first soaking portion 121 is silica gel (thermal conductivity: 0.35W/m·K), and the packaging material of the second soaking portion 122 is low-density polystyrene. Ethylene (thermal conductivity: 0.2-0.3W/m·K), and the packaging material of the third soaking portion 123 is low-density silica gel (thermal conductivity: 0.12W/m·K).
实施例6Example 6
与实施例4的区别在于：步骤(1)中，第二均热部122的厚度为15μm，第三均热部123的厚度为20μm。The difference from Embodiment 4 is that in step (1), the thickness of the second heat soaking portion 122 is 15 μm, and the thickness of the third heat soaking portion 123 is 20 μm.
上述实施例4-6与对比例1-2的各参数设置及测试结果见表2。The parameter settings and test results of the above-mentioned Examples 4-6 and Comparative Examples 1-2 are shown in Table 2.
表2Table 2
实施例7Example 7
与实施例1的区别在于：步骤(1)中，第一均热部121和第二均热部122均采用高密度聚乙烯(热传导系数：0.4W/m·K-0.5W/m·K，厚度10μm)封装后，第二均热部122再多封装一层低密度聚乙烯(热传导系数：0.2-0.3W/m·K)，厚度10μm，因此，通过热封的方式完成封装后，最终第一均热部121的封装厚度为10μm，第二均热部122的厚度为20μm(10μm+10μm)。The difference with Embodiment 1 is: in step (1), the first heat equalizing portion 121 and the second heat equalizing portion 122 are all made of high-density polyethylene (thermal conductivity: 0.4W/m K-0.5W/m K , thickness 10 μm) after packaging, the second heat soaking part 122 is packaged with a layer of low-density polyethylene (thermal conductivity: 0.2-0.3 W/m·K), thickness 10 μm, therefore, after the packaging is completed by heat sealing, Finally, the package thickness of the first heat soaking portion 121 is 10 μm, and the thickness of the second heat soaking portion 122 is 20 μm (10 μm+10 μm).
实施例1、实施例7与对比例1的各参数设置及测试结果见表3。The parameter settings and test results of Embodiment 1, Embodiment 7 and Comparative Example 1 are shown in Table 3.
表3table 3
实施例8Example 8
与实施例1的区别在于：步骤(1)中，加热部11的材质为镍片。The difference from Embodiment 1 is that in step (1), the heating part 11 is made of nickel sheet.
实施例1、实施例8与对比例1的各参数设置及测试结果见表4。The parameter settings and test results of Embodiment 1, Embodiment 8 and Comparative Example 1 are shown in Table 4.
表4Table 4
实施例9Example 9
与实施例1的区别在于：步骤(1)中，加热部11的厚度为30μm。The difference from Example 1 is that in step (1), the thickness of the heating part 11 is 30 μm.
实施例1、实施例9与对比例1的各参数设置及测试结果见表5。The parameter settings and test results of Embodiment 1, Embodiment 9 and Comparative Example 1 are shown in Table 5.
表5table 5
实施例10Example 10
与实施例1区别在于：步骤(6)中，加热部11的加热方式改成内部供电，即电化学装置中的控制电路处于导通状态，第一极耳13和第二极耳14分别通过所述控制电路与电化学装置中的正极极耳和负极极耳电连接，通过电化学装置内部施加电流从而实现所述加热部的加热功能。The difference from Example 1 is that in step (6), the heating mode of the heating part 11 is changed to an internal power supply, that is, the control circuit in the electrochemical device is in a conduction state, and the first tab 13 and the second tab 14 respectively pass through The control circuit is electrically connected to the positive pole lug and the negative pole pole lug in the electrochemical device, and the heating function of the heating part is realized by applying an electric current inside the electrochemical device.
实施例1、实施例10与对比例1的各参数设置及测试结果见表6。The parameter settings and test results of Embodiment 1, Embodiment 10 and Comparative Example 1 are shown in Table 6.
表6Table 6
实施例11Example 11
与实施例1区别在于：步骤(5)中，电芯的制备方式为叠片。The difference from Example 1 is that in step (5), the cell is prepared in the form of lamination.
实施例1、实施例11与对比例1的各参数设置及测试结果见表7。The parameter settings and test results of Example 1, Example 11 and Comparative Example 1 are shown in Table 7.
表7Table 7
由实施例1-11以及对比例1-2的数据可知，与采用具有均一的热传导能力的 绝缘材料对加热部进行封装相比，本申请中对产热高温度高的加热部采用具有低热传导能力的绝缘材料封装，对产热低温度低的加热部采用具有高热传导能力的绝缘材料封装，充分利用了加热部本身的产热，可促进加热部本身温度高的部位向温度低的部位导热，进而可以有效降低电化学装置表面的最大温差，即有效改善了电化学装置温度不均匀的问题。From the data of Examples 1-11 and Comparative Examples 1-2, it can be seen that compared with the use of an insulating material with uniform thermal conductivity to package the heating part, the heating part with high heat generation and high temperature is used in this application. High-performance insulating material packaging, the heating part with low heat generation and low temperature is packaged with insulating material with high thermal conductivity, making full use of the heat generation of the heating part itself, which can promote heat conduction from the high temperature part of the heating part itself to the low temperature part , which in turn can effectively reduce the maximum temperature difference on the surface of the electrochemical device, that is, effectively improve the problem of uneven temperature of the electrochemical device.
本申请提供的电化学装置，根据其表面的温度分布特性，对内置的加热组件采用具有不同热传导能力的绝缘材料进行封装。在加热组件的加热部产热低温度低的部位采用具有高热传导能力的绝缘材料封装，在产热高温度高的部位采用具有低热传导能力的材质封装，可以削减产热高的部位沿Z轴方向(加热部的内部向均热部的表面方向，即电化学装置的厚度方向)的热传导能力，并且在温差的作用下，会促进一部分热量通过加热部沿X轴方向(电化学装置的长度方向)和Y轴方向(电化学装置的宽度方向)朝温度低的部位传导，从而提高温度低的部位的温度。本申请提供的电化学装置可充分利用加热部产生的热量，有效降低加热部表面的温度差异性，最终实现加热部的快速升温和均匀产热，进而改善电化学装置的温度均匀性。In the electrochemical device provided by the present application, the built-in heating components are packaged with insulating materials with different thermal conductivity according to the temperature distribution characteristics of the surface. The parts with low heat generation and low temperature of the heating part of the heating element are packaged with insulating materials with high thermal conductivity, and the parts with high heat generation and high temperature are packaged with materials with low thermal conductivity, which can reduce the parts with high heat generation along the Z-axis Direction (the inside of the heating part to the surface of the heat soaking part, that is, the thickness direction of the electrochemical device), and under the action of temperature difference, it will promote a part of the heat to pass through the heating part along the X-axis direction (the length of the electrochemical device) direction) and the Y-axis direction (the width direction of the electrochemical device) conduct toward the low-temperature part, thereby increasing the temperature of the low-temperature part. The electrochemical device provided by the present application can make full use of the heat generated by the heating part, effectively reduce the temperature difference on the surface of the heating part, and finally achieve rapid heating and uniform heat generation of the heating part, thereby improving the temperature uniformity of the electrochemical device.
Claims (10)
- 一种电化学装置，其特征在于，包括加热组件，所述加热组件包括：A kind of electrochemical device, it is characterized in that, comprises heating assembly, and described heating assembly comprises:加热部，以及heating section, and围绕所述加热部设置的均热部；a heat soaking part arranged around the heating part;所述均热部包括互不重叠的第一均热部和第二均热部，所述第一均热部和所述第二均热部的热阻值倒数之比大于或等于1.05，所述第一均热部和所述第二均热部的面积分别大于2cm 2。 The heat equalizing portion includes a first heat equalizing portion and a second heat equalizing portion that do not overlap each other, and the ratio of the reciprocal of the thermal resistance of the first heat equalizing portion to the second heat equalizing portion is greater than or equal to 1.05, so The areas of the first heat soaking portion and the second heat soaking portion are respectively greater than 2 cm 2 .
- 如权利要求1所述的电化学装置，其特征在于，所述热阻值倒数的计算公式为C＝λS/L，其中，λ为均热部的热传导系数，L为均热部的厚度，S为均热部的面积。The electrochemical device according to claim 1, wherein the formula for calculating the reciprocal of the thermal resistance value is C=λS/L, where λ is the thermal conductivity coefficient of the heat soaking portion, and L is the thickness of the heat soaking portion, S is the area of the soaking portion.
- 如权利要求2所述的电化学装置，其特征在于，所述加热部的电阻率范围为10 -8Ω·m至10 -5Ω·m，所述加热部的厚度为1μm至80μm；所述均热部的热传导系数范围为0.1W/m·K至100W/m·K，所述均热部的厚度范围为1μm至80μm。 The electrochemical device according to claim 2, wherein the resistivity of the heating part ranges from 10 -8 Ω·m to 10 -5 Ω·m, and the thickness of the heating part is 1 μm to 80 μm; The thermal conductivity of the heat soaking portion ranges from 0.1 W/m·K to 100 W/m·K, and the thickness of the heat soaking portion ranges from 1 μm to 80 μm.
- 如权利要求1所述的电化学装置，其特征在于，所述均热部还包括第一均热部、第二均热部…和第N均热部，其中N是大于或等于3的整数，第一均热部的热阻值倒数＞第二均热部的热阻值倒数＞…＞第N均热部的热阻值倒数。The electrochemical device according to claim 1, wherein the heat soaking part further comprises a first heat soaking part, a second heat soaking part ... and an Nth heat soaking part, wherein N is an integer greater than or equal to 3 , the reciprocal of the thermal resistance of the first soaking portion>the reciprocal of the thermal resistance of the second soaking portion>…>the reciprocal of the thermal resistance of the Nth soaking portion.
- 如权利要求1所述的电化学装置，其特征在于，所述加热部的材质包括金属材料、碳系导电材料、金属氧化物或导电高分子材料中的至少一种。The electrochemical device according to claim 1, wherein the material of the heating part comprises at least one of a metal material, a carbon-based conductive material, a metal oxide, or a conductive polymer material.
- 如权利要求5所述的电化学装置，其特征在于，The electrochemical device according to claim 5, wherein,所述金属材料包括镍、钛、铜、金、银、铂、铁、钴、铬、钨、钼、铝、镁、钾、钠、钙、锶、钡、硅、锗、锑、铅、铟、锌或上述元素构成的组合物中的至少一种；The metal materials include nickel, titanium, copper, gold, silver, platinum, iron, cobalt, chromium, tungsten, molybdenum, aluminum, magnesium, potassium, sodium, calcium, strontium, barium, silicon, germanium, antimony, lead, indium , zinc or at least one of a combination of the above elements;所述碳系导电材料包括炭黑、石墨、石墨烯、碳纤维、单壁碳纳米管或多壁纳米管中的至少一种；The carbon-based conductive material includes at least one of carbon black, graphite, graphene, carbon fiber, single-walled carbon nanotubes or multi-walled nanotubes;所述金属氧化物包括掺铝氧化锌、掺钙铬酸镧、二氧化锡、掺氟二氧化锡、掺锑二氧化锡、氧化铟锡、掺银氧化铟锡或掺银合金氧化铟锡中的至少一种；The metal oxide includes aluminum-doped zinc oxide, calcium-doped lanthanum chromate, tin dioxide, fluorine-doped tin dioxide, antimony-doped tin dioxide, indium tin oxide, silver-doped indium tin oxide or silver-doped alloy indium tin oxide at least one of所述导电高分子材料包括聚乙炔、聚吡咯、聚噻吩、聚对苯、聚苯乙炔、聚苯胺或其掺杂高分子材料中的至少一种，所述掺杂高分子材料中的掺杂剂包括氯、碘、溴、氯化碘、溴化碘、氟化碘、五氟化磷、氢氟酸、盐酸、硝酸、硫酸、高氯酸、五氟化钼、五氟化钨、四氯化钛、四氯化锆、氯化铁或四碘化锡中的至少一种。The conductive polymer material includes at least one of polyacetylene, polypyrrole, polythiophene, polyparaphenylene, polyphenylene vinylene, polyaniline or its doped polymer material, and the doping in the doped polymer material Agents include chlorine, iodine, bromine, iodine chloride, iodine bromide, iodine fluoride, phosphorus pentafluoride, hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, molybdenum pentafluoride, tungsten pentafluoride, At least one of titanium chloride, zirconium tetrachloride, ferric chloride or tin tetraiodide.
- 如权利要求1所述的电化学装置，其特征在于，所述均热部的材质包括导热硅脂、硅胶、导热泥、灌封胶、ABS塑料、软质和硬质PVC、石蜡、石棉、硬木、软木、UP树脂、有机玻璃、聚碳酸酯、尼龙、聚乙烯、聚丙烯、异丁烯、聚酰胺、聚酰亚胺、聚硫胶、聚酯树脂、聚亚胺脂树脂、氯丁橡胶、聚酯马海毛、人造橡胶泡沫、聚氨酯、环氧树脂、聚苯硫醚塑料、聚酰胺、石墨、三氧化二铝、氧化镁、氧化锌或氧化镍中的至少一种。The electrochemical device according to claim 1, wherein the material of the soaking portion includes thermally conductive silicone grease, silica gel, thermally conductive mud, potting glue, ABS plastic, soft and hard PVC, paraffin, asbestos, Hardwood, cork, UP resin, plexiglass, polycarbonate, nylon, polyethylene, polypropylene, isobutylene, polyamide, polyimide, polysulfide, polyester resin, polyurethane resin, neoprene, At least one of polyester mohair, artificial rubber foam, polyurethane, epoxy resin, polyphenylene sulfide plastic, polyamide, graphite, aluminum oxide, magnesium oxide, zinc oxide, or nickel oxide.
- 如权利要求1-7任一项所述的电化学装置，其特征在于，所述加热组件包括第一极耳和第二极耳，所述第一极耳和所述第二极耳均设置于所述加热部上，且均与所述加热部电连接。The electrochemical device according to any one of claims 1-7, wherein the heating assembly comprises a first tab and a second tab, and the first tab and the second tab are both provided with on the heating part and are electrically connected to the heating part.
- 如权利要求8所述的电化学装置，其特征在于，所述电化学装置还包括正极极片和负极极片，所述加热组件与所述正极极片或所述负极极片相接触。The electrochemical device according to claim 8, characterized in that, the electrochemical device further comprises a positive pole piece and a negative pole piece, and the heating assembly is in contact with the positive pole piece or the negative pole piece.
- 一种二次电池，包括如权利要求9所述的电化学装置、温度感应装置、以及与所述温度感应装置和所述加热组件相连接的控制***，A secondary battery, comprising the electrochemical device according to claim 9, a temperature sensing device, and a control system connected to the temperature sensing device and the heating assembly,所述控制***可根据所述温度感应装置检测到的温度，控制加热组件所处电路处于导通或断开状态。The control system can control the circuit where the heating component is located to be on or off according to the temperature detected by the temperature sensing device.
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| WO2013115312A1 (en) * | 2012-02-02 | 2013-08-08 | 日産自動車株式会社 | Electrical device module |
| CN106816671A (en) * | 2015-12-01 | 2017-06-09 | 宁德时代新能源科技股份有限公司 | Battery unit, battery module and battery pack |
| CN107078313A (en) * | 2014-09-19 | 2017-08-18 | 马勒国际有限公司 | Heat exchanger for the temperature of the energy-storage travelling wave tube that controls accumulator |
| WO2021009957A1 (en) * | 2019-07-12 | 2021-01-21 | 古河電池株式会社 | Non-aqueous electrolyte secondary battery |
| CN112599785A (en) * | 2021-03-03 | 2021-04-02 | 浙江艾罗网络能源技术股份有限公司 | Self-temperature-control current collector of lithium ion battery and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013115312A1 (en) * | 2012-02-02 | 2013-08-08 | 日産自動車株式会社 | Electrical device module |
| CN107078313A (en) * | 2014-09-19 | 2017-08-18 | 马勒国际有限公司 | Heat exchanger for the temperature of the energy-storage travelling wave tube that controls accumulator |
| CN106816671A (en) * | 2015-12-01 | 2017-06-09 | 宁德时代新能源科技股份有限公司 | Battery unit, battery module and battery pack |
| WO2021009957A1 (en) * | 2019-07-12 | 2021-01-21 | 古河電池株式会社 | Non-aqueous electrolyte secondary battery |
| CN112599785A (en) * | 2021-03-03 | 2021-04-02 | 浙江艾罗网络能源技术股份有限公司 | Self-temperature-control current collector of lithium ion battery and preparation method and application thereof |
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