CN112316652B - Gas adsorption member and lithium ion battery - Google Patents
Gas adsorption member and lithium ion battery Download PDFInfo
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- CN112316652B CN112316652B CN201910716187.8A CN201910716187A CN112316652B CN 112316652 B CN112316652 B CN 112316652B CN 201910716187 A CN201910716187 A CN 201910716187A CN 112316652 B CN112316652 B CN 112316652B
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- B01D53/34—Chemical or biological purification of waste gases
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a gas adsorption member and a lithium ion battery. The gas adsorbing member of the present invention comprises an adsorbent comprising a CO as a CO, and a coating for forming a gas-permeable coating on the adsorbent2Hydroxide and/or strong base and weak acid salt of the absorbent; oxides as water absorbers; a halide catalyst supported on a porous carrier. The present invention also provides a lithium ion battery comprising the above gas adsorbing member. The gas adsorption component can realize the aim of adsorbing CO and CO2The double adsorption of the lithium ion battery reduces the air pressure in the lithium ion battery, reduces the degree of battery core bulging and interface impedance increase, and prolongs the service life of the lithium ion battery; can also adsorb CO and CO2And the moisture generated in the process is adsorbed, so that the negative influence of the moisture on the performance of the lithium ion battery is prevented.
Description
Technical Field
The invention relates to the field of batteries, in particular to a gas adsorption component and a lithium ion battery.
Background
In recent years, new energy automobiles are developed vigorously due to the characteristics of energy conservation and environmental protection, a battery driving system is a main factor influencing the performance and the cost of the new energy automobiles, and a power lithium ion battery is an important component of the battery driving system. Generally, a lithium ion battery includes a positive electrode, a negative electrode assembly, and an electrolyte sealed within a battery case. In the field of passenger vehicles, lithium ion batteries using a ternary nickel-cobalt-manganese material (NCM) as a positive electrode have become the mainstream of the market, because the energy density of the NCM is higher than that of lithium iron phosphate (LFP), more energy can be provided in a limited space, and mileage anxiety can be overcome. However, the technical problems to be solved in the lithium ion battery of the NCM system, such as the gas generation problem, are still more serious especially in the high nickel system. Excessive gas generation will cause the cell to swell, thereby causing the impedance of the battery to increase and the service life to be shortened.
The gas production mechanism inside the battery is complex, and has certain relation with the positive electrode, the negative electrode and the electrolyte, such as the reaction of the decomposition product of lithium salt and the electrolyte, the repair of SEI film, the reaction of miscellaneous lithium in the cathode and the electrolyte, the oxidation of the electrolyte by the positive electrode, and the like.
Generally, a battery manufacturer forms an inorganic salt protective film on the surface of a cathode and an anode by improving the formula of an electrolyte to reduce side reactions of the cathode and the anode at high temperature, thereby reducing gas generation, but the inorganic salt protective film formed in the method has high impedance and poor wettability, and an additive for improving the impedance and the wettability needs to be additionally added for synergistic action, so that the complexity and the cost of components in the electrolyte are greatly improved.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a gas adsorbing member and a lithium ion battery to improve the gas generation problem of the lithium ion battery.
In order to achieve the above object, a first aspect of the present invention provides a gas adsorbing member comprising an adsorbent and a cover forming a gas permeable coating on the adsorbent, the adsorbent comprising: as CO2Hydroxide and/or strong base and weak acid salt of the absorbent; oxides as water absorbers; a halide catalyst supported on a porous carrier. The inventor finds that main components of gas generated in the lithium ion battery are CO and CO through experiments2Therefore, the adsorbent designed for the two gases can effectively improve the gas expansion problem of the lithium ion battery cell.
A second aspect of the invention provides a lithium ion battery comprising the gas adsorbing member provided by the first aspect of the invention; the gas adsorption member is sealed in the battery case together with the electrode assembly and the electrolyte.
Compared with the prior art, the gas adsorption component provided by the invention can realize the effect of adsorbing CO and CO2The double adsorption of the lithium ion battery reduces the air pressure in the lithium ion battery, reduces the degree of battery core bulging and interface impedance increase, and prolongs the service life of the lithium ion battery; also adsorbing CO and CO2And the moisture generated in the process is adsorbed, so that the negative influence of the moisture on the performance of the lithium ion battery is prevented.
Detailed Description
The gas adsorption member and the lithium ion battery according to the present invention will be described in detail below.
First, a gas adsorbing member according to a first aspect of the present invention is explained, which comprises an adsorbent and a cover forming a gas-permeable coating on the adsorbent, the adsorbent comprising: as CO2Hydroxide and/or strong base weak acid salt of absorbent, oxide as water absorbent, halide catalyst supported on porous carrier.
In lithium ion batteries (particularly in high nickel systems with NCM as the positive electrode material), the gas generated in the battery is CO and CO2Has the highest ratio of CO gas to CO2The gases can be converted into each other, namely CO can be oxidized into CO under certain conditions2，CO2Will also be reduced to CO under certain conditions, and therefore only CO will be adsorbed or only CO will be adsorbed2The effect of performing adsorption is not optimal.
The gas adsorption component provided by the invention can realize the aim of adsorbing CO and CO2Double adsorption of (2). CO and CO in lithium ion batteries2The gas enters the gas adsorption member through the gas-permeable covering, on the one hand, as CO2Hydroxide or strong base weak acid salt of absorbent and CO2Reacting to generate water; alternatively, a hydroxide or a weak acid salt of a strong base with CO2The water produced by the reaction can initiate the catalytic oxidation of CO by the halide, and the halide loaded on the porous carrier is used as a catalyst to catalytically convert CO into CO2At the same time, equimolar water is also produced. The hydroxide or the strong base weak acid salt continuously absorbs CO catalytically converted from CO2And the oxide absorbs water generated by catalytic conversion of CO to prevent moisture from adversely affecting the performance of the lithium ion battery. Through the process, the gas adsorption component can realize the effect of adsorbing CO and CO in the lithium ion battery2The adsorption of the gas reduces the air pressure in the battery cell, reduces the swelling of the battery cell and the increase of the interface impedance, and prolongs the service life of the lithium ion battery; can also adsorb CO and CO2The moisture generated in the process of (2) is adsorbed, so that the negative influence of the moisture on the performance of the lithium ion battery is prevented.
As absorbents for CO2The kind of hydroxide and/or strong base weak acid salt, oxide as water absorbent and halide catalyst supported on porous carrier can affect CO and CO2Adsorption effect of two gases.
The hydroxide is selected from alkali metal hydroxide and/or alkaline earth metal hydroxide; preferably, the hydroxide is selected from one or more of lithium hydroxide, sodium hydroxide, calcium hydroxide, potassium hydroxide, magnesium hydroxide and barium hydroxide.
The strong alkali weak acid salt is selected from one or more of sodium metaaluminate, potassium metaaluminate, magnesium metaaluminate, calcium metaaluminate, sodium acetate and potassium acetate.
The oxide is selected from alkali metal oxide and/or alkaline earth metal oxide; preferably, the oxide is selected from one or more of lithium oxide, sodium oxide, calcium oxide, potassium oxide, magnesium oxide and barium oxide.
The halide is selected from one or more of cupric chloride, cuprous chloride, cupric bromide, cuprous bromide, cupric iodide, cuprous iodide, silver chloride, ferric chloride, ferrous chloride, nickel chloride, palladium chloride and zinc chloride.
CO2The molar ratio of the absorbent to the water absorbent affects the adsorption effect of the gas of the lithium ion battery, and CO2Adsorption of CO by absorbent2The generated moisture may have a great influence on the performance of the lithium ion battery, and the water adsorbent is required to adsorb the generated moisture, so that the CO needs to be controlled in order to effectively absorb the moisture and avoid unnecessary waste2The molar ratio of absorbent to the water absorbent is in a suitable range. Preferably, the CO is2The molar ratio of the absorbent to the water absorbent is 1: 3-3: 2, further preferably, the CO2The molar ratio of the absorbent to the water absorbent is 1:2 to 1: 1.
Mass of halide and CO2The mass ratio of the absorbent to the water absorbent affects the adsorption effect of the lithium ion battery gas, and the mass of the halide affects the conversion of CO into CO2In order to enable efficient conversion of CO, reasonable control is requiredThe quality of the halide, which affects the CO conversion, further affects the CO after conversion2Further influencing the CO after conversion2The absorption of the water produced after absorption, and therefore reasonable control of the halide mass and the CO is required2The mass ratio of the absorbent to the water absorbent can improve the overall adsorption performance of the adsorbent. Preferably, the mass of the halide is in combination with the CO2The mass ratio of the absorbent to the water absorbent is 0.2 to 2, and more preferably, the mass of the halide to the CO2The mass ratio of the absorbent to the water absorbent is 0.5 to 1.
The selection of the porous carrier influences the adsorption effect of the lithium ion battery gas, different types of porous carriers have larger differences in specific surface areas and surface free energies, and different molecular sieves influence the distribution and catalytic performance of halides, so that the porous carriers need to be reasonably selected.
Preferably, the porous carrier is selected from one or more of A-type molecular sieve, Y-type molecular sieve, X-type molecular sieve, ZSM-type molecular sieve, aluminum phosphate molecular sieve, activated carbon and silica gel.
The pore diameter of the porous carrier influences the adsorption effect of the lithium ion battery gas, and halide is loaded on the surface of the porous carrier and is mainly used for converting CO into CO2Therefore, the pore size of the porous carrier needs to be such that CO and CO are present2The electrolyte in the lithium ion battery is easy to diffuse to the porous carrier due to the diffusion effect, so that not only is the electrolyte unnecessarily lost, but also halide loaded by the porous carrier is inactivated, and therefore, the pore diameter of the porous carrier needs to be reasonably controlled, so that electrolyte molecules cannot enter pore channels of the porous carrier, and the adsorption effect is effectively improved.
Preferably, the pore size of the porous support is
Further preferably, the pore size of the porous support is
So that the gas adsorption member of the present invention adsorbs only CO2And catalytically converting the CO gas without adsorbing electrolyte vapor.
The specific surface area of the porous carrier influences the adsorption effect of the gas of the lithium ion battery. Preferably, the porous support has a specific surface area of 400m2/g～1000m2Per g, preferably 800m2/g～1000m2The effective contact area of the halide catalyst and the gas generated in the lithium ion battery is large enough, and the gas adsorption effect is ensured. The specific surface area of the porous support can be measured using instruments conventional in the art, such as: detecting by using a specific surface area analyzer BET and an equipment model Tri starII according to the following detection criteria: the specific surface area GB/T19587-2004 of the solid substance is measured by a gas adsorption BET method.
If the mass ratio of the halide to the carrier is too low, the catalytic effect is not good, resulting in poor absorption effect of the gas adsorption member of the present invention; if the mass ratio of the halide to the carrier is too high and the halide is excessive, part of the halide will not be uniformly distributed on the surface of the carrier, and the catalytic effect of the halide in the excess part will be very poor.
Preferably, the mass ratio of the halide to the porous support is 1: 1-1: 10, preferably 1: 3-1: 6.
preferably, the wrapping film is a breathable film; preferably selected from microporous membranes, woven membranes, nonwoven membranes, fibrous paper, rolled membranes or composite membranes of the above. The pore diameter of the breathable film is
Preferably, it is
In addition, the tensile strength of the breathable film is higher than 30MPa, so that the packaging reliability is ensured.
The lithium ion battery of the second aspect of the invention comprises a gas adsorbing member as described in the first aspect of the invention; the gas adsorption member is sealed in the battery case together with the electrode assembly and the electrolyte.
Among them, the electrode assembly and the electrolyte sealed in the battery case together with the gas adsorption member of the present invention may be conventionally selected in the art. For example, the electrode assembly may include a positive electrode tab, a negative electrode tab, a separator interposed between the positive electrode tab and the negative electrode tab; the electrolyte may also be any of a variety of electrolytes suitable for use in lithium ion batteries in the art.
Preferably, in the lithium ion battery provided by the invention, the ratio of the total mass of the adsorbent to the cell capacity is 4 × 10-5mol/Ah～8×10-4mol/Ah, preferably 8X 10-5mol/Ah～2×10-4mol/Ah。
The gas adsorption component and the lithium ion battery can be prepared by the following method:
(1) dissolving halide in a solvent in an air-isolated environment, soaking a porous carrier in the mixed solution in which the halide is dissolved, and drying to prepare a halide catalyst loaded by the porous carrier;
(2) taking the halide catalyst loaded on the porous carrier, and mixing the halide catalyst with CO2Mixing hydroxide and/or strong base weak acid salt of the absorbent and oxide serving as a water absorbent to obtain an absorbent;
(3) and packaging the adsorbent by using a breathable film to prepare the gas adsorption member.
(4) And sealing the gas adsorption member, the electrode assembly and the electrolyte in a battery shell to obtain the lithium ion battery.
Wherein the air-isolated environment may be in a nitrogen atmosphere, an inert gas atmosphere, or a vacuum. The solvent used to dissolve the halide may be selected from water, dilute hydrochloric acid or concentrated hydrochloric acid; in the step of soaking the porous carrier in a mixed solution in which halide is dissolved, the mass percentage of the halide in the mixed solution can be 5-60%; the soaking time can be 0.1-36 h; the drying temperature can be 30-200 ℃; the drying time can be 2-36 h.
The present application is further illustrated with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.
Examples 1 to 21 and comparative examples 1 to 4
And dissolving halide in water in the whole argon atmosphere, soaking porous carrier powder in the aqueous solution of the halide, and drying to obtain the halide catalyst loaded by the porous carrier. Taking halide catalyst and CO loaded on porous carrier2The absorbent and the water absorbent are uniformly mixed, encapsulated in the cladding and assembled in the top sealing space of the battery core. Table 1 shows specific parameters of examples 1 to 21 and comparative examples 1 to 4.
In order to verify the technical effect of the invention, the lithium ion batteries prepared in the examples 1 to 21 and the comparative examples 1 to 4 were tested as follows:
1. days required for air pressure in the battery cell to reach 0.35MPa
And connecting a pressure gauge on the top cover of the battery cell, after counting and resetting, placing the battery cell in a high-low temperature box at the temperature of 70 ℃, standing, reading the reading of the pressure gauge every day until the reading of the pressure gauge is displayed to be 0.35MPa, and recording the days taken when the reading of the pressure gauge reaches 0.35 MPa.
2. Gas adsorption Rate (mmol/h)
Placing 5g of the gas adsorbent in a closed space, filling carbon monoxide gas CO into the closed space to a positive pressure of 0.1MPa, standing for 2-8 h, monitoring the air pressure in real time, and finally calculating to obtain the adsorption rate.
The results of the performance tests of examples 1-21 and comparative examples 1-4 are also given in Table 1 below.
From the data in table 1 it can be seen that:
examples 1 to 21 are examples including a gas adsorbing member, and comparative examples 1 to 4 are comparative examples not including a gas adsorbing member. In examples 1 to 21, the number of days required for the gas pressure in the cell to reach 0.35MPa and the results of gas adsorption rate detection were all superior to those in comparative examples 1 to 4, because the gas adsorption member of the present invention adsorbed lithiumCO, CO in ion battery2Gas and moisture are adsorbed, so that the air pressure in the battery cell is reduced, and the situations of battery cell bulging and interface impedance increase are effectively reduced.
Examples 1 to 7 discuss CO in the gas adsorbing member of the present invention2The influence of the molar ratio of the absorbent to the water absorbent on the technical effect. The days required for the air pressure in the battery core of the embodiments 1-5 to reach 0.35MPa and the detection result of the gas adsorption rate are obviously superior to those of the embodiments 6 and 7; meanwhile, in examples 1 to 5, the number of days required for the air pressure in the battery cell of examples 4 and 5 to reach 0.35MPa, and the gas adsorption rate detection result are superior to those in examples 1 to 3. Thus, CO2The molar ratio of absorbent to water absorbent is preferably in the range of 1: 3-3: 2, and more preferably 1:2 to 1: 1. When CO is present2When the absorbent is excessive, excessive water can be generated, and the performance and long-term reliability of the battery cell are affected; when the amount of the water absorbent is too large, CO cannot be completely absorbed2。
Examples 8 to 14 discuss the mass of halide and CO in the gas adsorbing member of the present invention2The influence of the sum of the mass of the absorbent and the water absorbent on the technical effect. The days required for the air pressure in the battery core of the embodiments 8-12 to reach 0.35MPa and the detection result of the gas adsorption rate are superior to those of the embodiments 13 and 14; meanwhile, in examples 8 to 12, the number of days required for the air pressure in the battery cell of examples 11 and 12 to reach 0.35MPa was superior to that in examples 8 to 10 in the detection result of the gas adsorption rate. Thus, in the present invention, the mass of halide and CO2The mass ratio of the absorbent to the water absorbent is preferably in the range of 0.2 to 2, and more preferably 0.5 to 1, thereby ensuring efficient absorption of CO and CO as much as possible2And water. If the halide is too much, the halide will remain and CO2Can not be completely absorbed; such as CO2Excessive absorbent and water absorbent, CO2The absorbent and water absorbent will remain and the CO will not be fully absorbed.
Examples 15 to 21 discuss the influence of the mass ratio of the halide to the porous carrier on the technical effect in the gas adsorbing member of the present invention. The days required for the air pressure in the battery core of the embodiments 15-20 to reach 0.35MPa and the detection result of the gas adsorption rate are obviously superior to those of the embodiments 20 and 21; meanwhile, in examples 15 to 20,
the number of days required for the air pressure in the battery cell to reach 0.35MPa and the detection result of the gas adsorption rate of the battery cells of the embodiments 18 and 19 are better than those of the embodiments 15 to 17. Therefore, in the present invention, the mass ratio of the halide to the porous support is 1: 1-1: 10, preferably 1: 3-1: 6. when the mass ratio of the halide to the carrier is too low, the catalytic effect is poor, and the gas adsorption effect is poor; when the mass ratio of the halide to the carrier is too high and the halide is excessive, part of the halide cannot be uniformly distributed on the surface of the carrier, and the catalytic effect of the halide in the excessive part is extremely poor.
Variations and modifications to the above-described embodiments may occur to those skilled in the art based upon the disclosure and teachings of the above specification. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (16)
1. A gas adsorption member for a lithium ion battery, comprising an adsorbent and a coating forming a gas-permeable coating over the adsorbent, the adsorbent comprising:
as CO2Hydroxide and/or strong base and weak acid salt of the absorbent;
oxides as water absorbers;
a halide catalyst supported on a porous support;
the CO is2The molar ratio of the absorbent to the water absorbent is 1: 3-3: 2; mass of the halide and the CO2The mass ratio of the absorbent to the water absorbent is 0.2 to 2.
2. The gas adsorbing member for a lithium ion battery according to claim 1,
the hydroxide is selected from alkali metal hydroxide and/or alkaline earth metal hydroxide;
the strong base weak acid salt is selected from one or more of sodium metaaluminate, potassium metaaluminate, magnesium metaaluminate, calcium metaaluminate, sodium acetate and potassium acetate;
the oxide is selected from alkali metal oxide and/or alkaline earth metal oxide;
the halide is selected from one or more of cupric chloride, cuprous chloride, cupric bromide, cuprous bromide, cupric iodide, cuprous iodide, silver chloride, ferric chloride, ferrous chloride, nickel chloride, palladium chloride and zinc chloride.
3. The gas adsorbing member for a lithium ion battery according to claim 2,
the hydroxide is selected from one or more of lithium hydroxide, sodium hydroxide, calcium hydroxide, potassium hydroxide, magnesium hydroxide and barium hydroxide;
the oxide is selected from one or more of lithium oxide, sodium oxide, calcium oxide, potassium oxide, magnesium oxide and barium oxide.
4. The gas adsorbing member for a lithium ion battery according to claim 1,
the CO is2The molar ratio of the absorbent to the water absorbent is 1: 2-1: 1;
mass of the halide and the CO2The mass ratio of the absorbent to the water absorbent is 0.5 to 1.
5. The gas adsorption member for a lithium ion battery according to claim 1, wherein the porous support is one or more selected from a group consisting of an a-type molecular sieve, a Y-type molecular sieve, an X-type molecular sieve, a ZSM-type molecular sieve, an aluminum phosphate molecular sieve, activated carbon, and silica gel.
6. The gas adsorption member for a lithium ion battery according to claim 5, wherein pores of the porous supportHas a diameter of
7. The gas adsorption member for a lithium ion battery according to claim 6, wherein the pore size of the porous support is
8. The gas adsorption member for a lithium ion battery according to claim 5, wherein the specific surface area of the porous support is 400m2/g～1000m2/g。
9. The gas adsorption member for a lithium ion battery according to claim 8, wherein the specific surface area of the porous support is 800m2/g～1000m2/g。
10. The gas adsorption member for a lithium ion battery according to claim 1, wherein the mass ratio of the halide to the porous support is 1: 1-1: 10.
11. the gas adsorbing member for a lithium ion battery according to claim 10, wherein the mass ratio of the halide to the porous support is 1: 3-1: 6.
12. the gas adsorption member for a lithium ion battery according to claim 1, wherein the pore size of the gas-permeable covering is
13. The gas adsorption member for a lithium ion battery according to claim 12, whichCharacterized in that the pore diameter of the coating of the air-permeable coating is
14. A lithium ion battery comprising the gas adsorbing member according to any one of claims 1 to 13; the gas adsorption member is sealed in the battery case together with the electrode assembly and the electrolyte.
15. The lithium ion battery of claim 14, wherein the ratio of the total mass of the sorbent in the gas adsorbing member to the cell capacity is 4 x 10-5mol/Ah～8×10-4mol/Ah。
16. The lithium ion battery of claim 15, wherein the ratio of the total mass of the sorbent in the gas adsorbing member to the cell capacity is 8 x 10-5mol/Ah～2×10-4mol/Ah。
Priority Applications (2)
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| CN201910716187.8A CN112316652B (en) | 2019-08-05 | 2019-08-05 | Gas adsorption member and lithium ion battery |
| PCT/CN2020/106918 WO2021023197A1 (en) | 2019-08-05 | 2020-08-04 | Adsorbent composition, gas adsorbing member, lithium ion battery and device |
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| EP4131611A4 (en) * | 2021-05-28 | 2024-07-10 | Contemporary Amperex Technology Co Ltd | Gas adsorption apparatus, end cover assembly, battery cell, battery, and electrical device |
| WO2024036430A1 (en) * | 2022-08-15 | 2024-02-22 | 宁德时代新能源科技股份有限公司 | Negative electrode active material, negative electrode sheet, secondary battery, electric device, and preparation method |
| CN115498356A (en) * | 2022-09-30 | 2022-12-20 | 峰谷动力(深圳)新能源技术有限公司 | Lithium ion battery |
| CN115832580B (en) * | 2022-11-24 | 2024-09-06 | 宁德时代新能源科技股份有限公司 | Battery monomer, battery and power consumption device |
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| CN86102838B (en) * | 1986-04-26 | 1987-09-09 | 北京大学 | High-efficiency adsorbent and preparation method and application thereof |
| KR910002270B1 (en) * | 1989-04-07 | 1991-04-11 | 두산농산 주식회사 | Method of removing gas from vessel |
| ITMI20071147A1 (en) * | 2007-06-05 | 2008-12-06 | Getters Spa | RECHARGEABLE LITHIUM BATTERIES INCLUDING VEHICLES FOR THE ABSORPTION OF HARMFUL SUBSTANCES |
| WO2010025761A1 (en) * | 2008-09-02 | 2010-03-11 | Abb Research Ltd | System and method for fire protection |
| ITMI20121207A1 (en) * | 2012-07-11 | 2014-01-12 | Getters Spa | GETTER COMPOSITE FOR CARBON DIOXIDE |
| JP6221854B2 (en) * | 2013-05-20 | 2017-11-01 | 栗田工業株式会社 | Lithium ion battery and electronic device using the same |
| WO2014192094A1 (en) * | 2013-05-29 | 2014-12-04 | 日立オートモティブシステムズ株式会社 | Lithium ion secondary battery |
| ITMI20132216A1 (en) * | 2013-12-30 | 2015-07-01 | Getters Spa | GETTER COMPOSITE FOR CARBON DIOXIDE |
| CN109499261A (en) * | 2018-12-03 | 2019-03-22 | 四川天科技股份有限公司 | The removing system and method for CO in a kind of used in proton exchange membrane fuel cell hydrogen |
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