CN112467270B - Composite air suction element, preparation method thereof and flatulence-preventing self-repairing soft-package lithium battery - Google Patents
Composite air suction element, preparation method thereof and flatulence-preventing self-repairing soft-package lithium battery Download PDFInfo
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Abstract
The application relates to the field of lithium batteries, and particularly discloses a composite air suction element, a preparation method thereof and a soft package lithium battery capable of preventing flatulence and self repairing. The composite getter element is made from the following raw materials in parts by weightThe composition is as follows: electrolytic MnO 2 45‑55、Ag 2 O or Ag9.5-10.5, carbon-based conductive agent 3.5-5.5, activated carbon powder 13-17, binder 13-15, sodium sulfate 1-5, gas phase SiO 2 5-10; the preparation method comprises the following steps: mnO is to be electrolyzed 2 、Ag 2 Mixing O or Ag powder, carbon-based conductive agent and activated carbon powder uniformly, grinding, and dispersing to prepare slurry; adding a binder, sodium sulfate and gas-phase SiO into the slurry 2 Mixing to prepare a suspension, performing ultrasonic treatment on the suspension, then performing fixed-shape die casting, performing dynamic vacuum drying at room temperature, and cooling to room temperature to obtain a gas suction precursor; and performing surface hydrophobic and oleophobic treatment on the precursor element. The composite air suction element can be used for the soft package lithium battery with the anti-flatulence self-repairing function and has the advantage of the bulging self-repairing function.
Description
Technical Field
The application relates to the field of lithium batteries, in particular to a composite air suction element, a preparation method thereof and an anti-flatulence self-repairing soft package lithium battery.
Background
As the kinds and number of mobile electronic products continue to increase, the demand for secondary batteries continues to increase, and thus it is necessary and important to develop new rechargeable batteries.
The lithium ion battery has large energy density, high average output voltage and high charging efficiency, and is widely applied to digital products. Lithium ions are inserted into graphite to form a negative electrode, and LiCoO is commonly used as a positive electrode material 2 、Li x NiO 2 Or Li x MnO 4 LiPF for electrolyte 6 Anhydrous aprotic mixtures such as diethylene carbonate and dimethyl carbonate.
The polymer lithium ion battery core mostly adopts the packaging technology of the aluminum-plastic composite membrane, when the inside of the battery core generates gas due to the occurrence of abnormal chemical reaction, the package can be charged, and the battery core expands to cause the unusable battery. When the battery cell expands to a certain limit, explosion may be caused, which is very dangerous.
Disclosure of Invention
In order to solve the problem that a lithium battery is prone to bulging, the application provides a composite air suction element, a preparation method of the composite air suction element and a soft package lithium battery capable of preventing flatulence and self-repairing.
In a first aspect, the present application provides a composite getter element that employs the following technical solution:
a composite getter element is prepared from the following raw materials in parts by weight:
electrolytic MnO 2 45-55
Ag 2 9.5-10.5% of O or Ag
Carbon-based conductive agent 3.5-5.5
Activated carbon powder 13-17
13-15 parts of adhesive
Sodium sulfate 1-5
Gas phase SiO 2 5-8。
By adopting the technical scheme, when the battery is improperly produced with a small amount of gas, ag, in the battery due to the manufacturing process or the charging process 2 O or Ag and electrolytic MnO 2 And the active carbon absorbs the gas and the like generated by the battery under the combined action, so that the battery is prevented from bulging, and the battery has a bulge self-repairing function. Therefore, an excellent safety effect is obtained.
Preferably, said composite getter element consists, in parts by weight, of 50 parts of electrolytic MnO 2 10 parts of Ag 2 O or Ag, 4 parts of carbon-based conductive agent, 15 parts of activated carbon powder, 1 part of sodium sulfate, 14 parts of binder and 6 parts of gas-phase SiO 2 And (4) preparing.
By adopting the technical scheme, mnO is electrolyzed due to moderate proportion of raw materials 2 /Ag 2 The O/activated carbon ratio is 5. Due to the moderate binder material ratio, excellent integrity and integrity of the composite getter element is obtained. Due to gas phase SiO 2 The proportion of the raw materials is moderate, so that excellent specific surface area is obtained, and the transmission of gas in the composite gas suction element and the gas suction repair efficiency are ensured; therefore, the composite air suction element obtains a proper surface microstructure, and the composite air suction element and subsequent dipping treatment jointly form the hydrophobic and oleophobic characteristics of the composite air suction element, so that the pore structure in the composite air suction element is ensured, and the composite air suction element is prevented from being blocked by electrolyte or other liquid.
Preferably, the carbon-based conductive agent is a composition of conductive carbon black, conductive carbon nanotubes and graphene.
By adopting the technical scheme, the conductive carbon nano tube and the graphene are adopted, so that the internal specific surface area of the composite material is increased, the absorbed gas is oxidized when being favorable for later-stage discharge, the pressure generated by overcharge in the battery is reduced, and the safety of the battery is improved.
Preferably, the carbon-based conductive agent comprises conductive carbon black: conductive carbon nanotubes: the weight ratio of the graphene is 0.5-1.
By adopting the technical scheme, because the proportion of the carbon-based conductive agent raw materials is moderate, excellent electronic conductivity is obtained, and the MnO electrolysis of the composite air suction element in the gas decomposition process is ensured 2 /Ag 2 The action relationship and the synergy of the O/activated carbon.
Preferably, the carbon-based conductive agent comprises conductive carbon black: conductive carbon nanotubes: the weight ratio of graphene is 0.7.
By adopting the technical scheme, the conductive carbon nanotube and the graphene are 1:2, and good air suction performance is obtained.
Preferably, the binder is a polytetrafluoroethylene-based adhesive.
Through adopting above-mentioned technical scheme, owing to adopt the polytetrafluoroethylene adhesive, can play the bonding effect through less quantity to polytetrafluoroethylene can provide oleophobic characteristic.
In a second aspect, the present application provides a method for manufacturing a composite getter element, which adopts the following technical scheme:
a method for manufacturing a composite getter element, comprising the steps of:
s1: mnO is to be electrolyzed 2 、Ag 2 Mixing O, a carbon-based conductive agent and activated carbon powder uniformly, grinding the mixture to micron level, and dispersing the mixture into a solvent to prepare slurry;
s2: adding a binder, sodium sulfate and gas-phase SiO into the slurry obtained in the step S1 2 Uniformly mixing to prepare a suspension, carrying out ultrasonic treatment on the suspension, then pouring and shaping, carrying out dynamic vacuum drying at room temperature, and cooling to obtain a gas suction precursor;
s3: and (3) performing surface hydrophobic and oleophobic treatment on the gas absorption precursor in the step (S2) to obtain the composite gas absorption element.
Through adopting above-mentioned technical scheme, avoid producing obvious influence to laminate polymer battery's outward appearance to produce the guard action to electric core entity, improve the hardness and the rigidity of battery to a certain extent, reduce because of external force leads to the battery to warp or the short circuit, improve battery security performance. Since no calendering is performed, the specific surface area of the getter precursor is preserved to the maximum extent, and the surface has a high roughness and microstructure.
Preferably, in the step S3, the hydrophobic and oleophobic treatment is to dip at least one of an organic fluorine-containing material, an organic silicon material or an organic fluorine-silicon material on the surface of the inspiration precursor, the surface treatment temperature is 25-50 ℃, and the heat preservation is carried out for 3-24h.
By adopting the technical scheme, the organic material and the microstructure on the surface of the air suction precursor form the super-hydrophobic and oleophobic characteristic under the synergistic effect, so that the smoothness of the pore structure in the composite air suction element is ensured, and the composite air suction element is prevented from being blocked by electrolyte or other liquid. The obtained effect of surface treatment also has high and low temperature resistance (-60-300 ℃), oxidation degradation resistance, electrical insulation performance and flame retardance. During the impregnation process, na 2 SO 4 A dissolution reaction can occur to generate a microporous structure, which is beneficial to the opening of the air suction channel.
Preferably, the hydrophobic and oleophobic treatment mode is as follows: immersing the getter precursor into an isopropanol solution of 18-22% perfluoroheptyl sulfonyl aminoethyl trimethoxysilane, standing at 25 ℃ for 24h, taking out, washing and drying.
Preferably, the hydrophobic and oleophobic treatment mode is as follows: immersing the air-breathing precursor into 3-7% of ethanol solution of 3-aminobutyltrimethoxysilane, standing at 40 ℃ for 4h, taking out, cleaning and drying. More preferably, the dried getter precursor is immersed again in a 10% to 20% solution of perfluorobutanesulfonyl fluoride in toluene, left at 25 ℃ for 4 hours, then removed, washed and dried.
Preferably, the hydrophobic and oleophobic treatment mode is as follows: immersing the air-breathing precursor into 3-7% of ethanol solution of vinyl trimethoxy silane, standing at 40 ℃ for 4h, taking out, cleaning and drying; then the precursor is immersed in a toluene solution of 5% -15% of alkene butyl perfluoro (2-isopropyl-1,3-dimethyl-1-butenyl) ether, placed at 25 ℃ for 4h, taken out, cleaned and dried.
By adopting the technical scheme, the fluorine-containing olefin and the polydimethylsiloxane are subjected to hydrosilylation addition reaction to obtain the fluorine-silicon block copolymer, so that the surface of the obtained composite air suction element has good hydrophobic and oleophobic properties.
Preferably, the solid content of the slurry in the step S1 is 35-55%, and the particle size of the particles in the slurry is 100-200nm.
By adopting the technical scheme, the raw materials are ground into powder and uniformly dispersed, the slurry is easy to pour and form, the material precipitation is avoided in the forming process, the performance of the composite air suction element is relatively uniform, and the comprehensive reaction absorption performance of gas generated by the anode is improved.
In a third aspect, the application provides an anti-flatulence self-repairing soft-package lithium battery, which adopts the following technical scheme:
the utility model provides a soft packet of lithium cell of flatulence self-repairing is prevented, includes electric core, electrolyte and is used for the shell of encapsulation electrolyte, still includes the safety element of above-mentioned compound inspiration component preparation, and safety element is located between electric core and the shell.
Preferably, the negative electrode of the lithium battery is a lithium metal negative electrode or a negative electrode piece treated by a lithium supplementing process.
By adopting the technical scheme, when the battery generates a gassing phenomenon, the safety element with the hydrophobic and oleophobic characteristics between the battery core main body and the shell and the composite air suction element with the porous structure which is not blocked by electrolyte or other liquid in the whole life cycle can adsorb, store, react and consume gas, so that the safety of the battery is improved.
In summary, the present application has the following beneficial effects:
1. because the present application uses electrolytic MnO 2 、Ag 2 The O or Ag powder and the active carbon composite material absorb the gas precipitated by the reaction due to the electrolysis of MnO 2 Has high oxidizing property, ag 2 O has a catalytic action, and the activated carbon has stronger adsorption performance, thereby obtaining the effect of improving the safety of the battery by good air suction performance.
2. In addition, the method also has the function of absorbing gas-phase active groups of the battery in the thermal runaway process, adsorbs high-activity groups, and reduces the reaction activity, thereby improving the safety of the battery cell in the thermal runaway process.
3. The composite air suction element has the hydrophobic and oleophobic air permeability, so that the damage of moisture to the battery core main body after the battery is packaged and damaged by the aluminum plastic film can be reduced, and the liquid leakage rate of the battery core main body can be reduced.
4. The composite air suction element avoids obvious influence on the appearance of the soft package battery, and has a protection effect on the electric core entity, so that the hardness and rigidity of the battery are improved to a certain extent, the deformation or short circuit of the battery caused by external force is reduced, and the safety performance of the battery is improved.
5. The device can have an immune effect on the bulge in the whole life cycle of the battery, comprehensively avoid the battery inflation and prolong the service life of the battery.
6. The battery yield is improved, the battery scrap proportion is reduced, and the production efficiency and the resource utilization rate are improved.
Detailed Description
The present application will be described in further detail with reference to examples.
Lithium ion batteries are a widely used rechargeable battery. The polymer lithium ion battery core mostly adopts the packaging technology of an aluminum-plastic composite film, when gas is generated in the battery core due to the occurrence of abnormal chemical reaction, the package can be charged, and the battery core is swelled. In order to solve this problem, the applicant has conducted a great deal of research on battery production processes and found that the generation of the internal swelling gas in the battery is mainly normal formation gas generation and abnormal gas generation, and the battery cell normally generates a small amount of gas during formation starting, which varies depending on the raw materials used, and such gas is pumped out during the secondary packaging process. However, the subsequent abnormal gas generation can directly cause the battery to be scrapped so as to cause danger, mainly because of the following reasons:
(1) The water content in the battery core does not reach the standard: a. the pole piece battery core is insufficiently dried; b. the vacuum baking time of the battery is insufficient; c. the liquid injection glove box has low air tightness; d. the content of water and free acid in the electrolyte exceeds the standard; e. unreliable packaging results in the ingress of system-sensitive materials such as water and oxygen into the cell.
(2) Poor system control: a. the electrolyte and the anode are decomposed unstably; b. instability of the negative electrode SEI film; c. the formation process is not sufficient, and the gas production is not complete; e. the vacuum pumping is not thorough.
(3) Overcharge, overdischarge, and short circuit: the battery cell is overcharged or overdischarged due to an abnormality of a flow or a machine or a protective plate, and the battery cell may be inflated.
(4) And (3) high-temperature storage: on the one hand, the SEI film is unstable at high temperature, and on the other hand, the gas generation side reaction between the anode and the electrolyte is strengthened.
(5) Some special processes, such as a lithium supplement process in the middle of anode and cathode cycle, not only need to supplement lithium in the first formation process, but also need to supplement lithium in the middle of cycle in the practical application process, and the lithium supplement material is unstable or gas is generated through reaction in the lithium supplement process.
Based on the discovery, the applicant carries out a great deal of research on the structure and the production process of the battery, and as a result, the inventor discovers that when a small amount of gas is generated in the battery due to improper manufacturing process or charging process of the battery, the battery is prevented from bulging by the self-adsorption function of the composite gas suction element due to the fact that the composite gas suction element is added between the battery core main body and the aluminum-plastic package in the battery, and the battery has a bulging self-repairing function. The present application has been made based on the above findings.
Raw materials
Preparation example of carbon-based conductive agent
And (3) putting the conductive carbon black, the conductive carbon nano tube and the graphene powder into a stirrer, stirring and mixing for 20-30min, and sieving to obtain a carbon-based conductive agent with uniform components, wherein the particle size of the carbon-based conductive agent is not more than. The composition of the carbon-based conductive agent is shown in table 1.
TABLE 1 raw Material Components for preparation of carbon-based conductive agent
Examples
Example 1
A method for manufacturing a composite getter element, comprising the steps of:
s1: 50g of electrolytic MnO 2 10g of Ag 2 O, 4.5g of carbon-based conductive agent and 15g of activated carbon powder are uniformly mixed and ground for 30min, the particle size of the particles is 100-200nm, and then the particles are dispersed into 400ml of alcohol to prepare slurry, wherein the carbon-based conductive agent is the carbon-based conductive agent in preparation example 1, and the alcohol is 95% alcohol.
S2: to the slurry obtained in step S1 were added 14g of PVDF binder, 3g of sodium sulfate and 6.5g of gas-phase SiO 2 Uniformly mixing to prepare a suspension, carrying out ultrasonic treatment on the suspension for 3min, then pouring and shaping, and carrying out dynamic vacuum drying for 48h at 25 ℃ to obtain the gas-suction precursor. In other embodiments, the PVDF binder may also be replaced with a PTFE binder.
S3: and immersing the getter precursor into an isopropanol solution of 20% perfluoroheptyl sulfonyl aminoethyl trimethoxysilane, standing at 25 ℃ for 24 hours, taking out the getter precursor, cleaning and drying to obtain the composite getter element. The drying mode can be vacuum drying or N 2 Drying under atmosphere, or vacuum drying and then N 2 Drying in atmosphere or vacuum with N 2 The atmosphere drying is alternately performed. In this example, vacuum drying and N were used 2 The atmosphere drying is alternately performed.
Example 2
A method for manufacturing a composite getter element, comprising the steps of:
s1: 50g of electrolytic MnO 2 10g of Ag 2 O, 4.5g of carbon-based conductive agent and 13g of activated carbon powder are uniformly mixed and ground for 30min, the particle size of the particles is 100-200nm, and then the particles are dispersed into 370ml of alcohol to prepare slurry, wherein the carbon-based conductive agent is the carbon-based conductive agent prepared in preparation example 1, and the alcohol is used for ensuring that the carbon-based conductive agent is dissolved in the alcoholUsing 95% alcohol.
S2: to the slurry obtained in step S1 were added 13g of PVDF binder, 5g of sodium sulfate and 6.5g of gas-phase SiO 2 Uniformly mixing to prepare a suspension, carrying out ultrasonic treatment on the suspension for 2min, then pouring and shaping, and carrying out dynamic vacuum drying for 50h at 20 ℃ to obtain the air suction precursor.
S3: and immersing the getter precursor into an isopropanol solution of 18% perfluoroheptyl sulfonyl aminoethyl trimethoxysilane, standing at 20 ℃ for 24 hours, taking out the getter precursor, cleaning and drying to obtain the composite getter element. The drying mode can be vacuum drying or N 2 Drying under atmosphere, or vacuum drying and then N 2 Drying in atmosphere or vacuum with N 2 The atmosphere drying is alternately performed. In this example, vacuum drying and N were used 2 The atmosphere drying is alternately performed.
Example 3
A method for manufacturing a composite getter element, comprising the steps of:
s1: 50g of electrolytic MnO 2 10g of Ag 2 O, 4.5g of carbon-based conductive agent and 17g of activated carbon powder are uniformly mixed and ground for 30min, the particle size of the particles is 100-200nm, and then the particles are dispersed into 370ml of alcohol to prepare slurry, wherein the carbon-based conductive agent is the carbon-based conductive agent in preparation example 1, and the alcohol is 95% alcohol.
S2: to the slurry obtained in step S1 were added 15g of PVDF binder, 3g of sodium sulfate and 6.5g of gas-phase SiO 2 Uniformly mixing to prepare a suspension, carrying out ultrasonic treatment on the suspension for 4min, then pouring and shaping, and carrying out dynamic vacuum drying for 45h at 30 ℃ to obtain the gas-suction precursor.
S3: and immersing the getter precursor into an isopropanol solution of 22% perfluoroheptyl sulfonyl aminoethyl trimethoxysilane, standing at 20 ℃ for 24 hours, taking out the getter precursor, cleaning and drying to obtain the composite getter element. The drying mode can be vacuum drying or N 2 Drying under atmosphere, or vacuum drying and then N 2 Drying in atmosphere or vacuum with N 2 The atmosphere drying is alternately performed. In this embodiment, vacuum drying is adoptedDrying and N 2 The atmosphere drying is alternately performed.
Example 4
A method for manufacturing a composite getter element, comprising the steps of:
s1: 45g of electrolytic MnO 2 10g of Ag 2 O, 4.5g of carbon-based conductive agent and 15g of activated carbon powder are uniformly mixed and ground for 30min, the particle size of the particles is 100-200nm, and then the particles are dispersed into 400ml of alcohol to prepare slurry, wherein the carbon-based conductive agent is the carbon-based conductive agent in preparation example 1, and the alcohol is 95% alcohol.
S2: to the slurry obtained in step S1 were added 14g of PVDF binder, 5g of sodium sulfate and 6.5g of gas-phase SiO 2 Uniformly mixing to prepare a suspension, carrying out ultrasonic treatment on the suspension for 3min, then pouring and shaping, and carrying out dynamic vacuum drying for 45h at 30 ℃ to obtain the gas-suction precursor.
S3: and immersing the getter precursor into an isopropanol solution of 20% perfluoroheptyl sulfonyl aminoethyl trimethoxysilane, standing at 20 ℃ for 24 hours, taking out the getter precursor, cleaning and drying in vacuum to obtain the composite getter element.
Example 5
A method for manufacturing a composite getter element, comprising the steps of:
s1: 55g of electrolytic MnO 2 10g of Ag 2 O, 4.5g of carbon-based conductive agent and 15g of activated carbon powder are uniformly mixed and ground for 30min, the particle size of the particles is 100-200nm, and then the particles are dispersed into 400ml of alcohol to prepare slurry, wherein the carbon-based conductive agent is the carbon-based conductive agent in the preparation example 1, and the alcohol is 95% alcohol.
S2: to the slurry obtained in step S1 were added 15g of PVDF binder, 3g of sodium sulfate and 6.5g of gas-phase SiO 2 Uniformly mixing to prepare a suspension, carrying out ultrasonic treatment on the suspension for 3min, then pouring and shaping, and carrying out dynamic vacuum drying for 48h at 25 ℃ to obtain the gas-suction precursor.
S3: and immersing the getter precursor into an isopropanol solution of 20% perfluoroheptyl sulfonyl aminoethyl trimethoxysilane, standing at 20 ℃ for 24 hours, taking out the getter precursor, cleaning and drying in vacuum to obtain the composite getter element.
Example 6
A method for manufacturing a composite getter element, comprising the steps of:
s1: 55g of electrolytic MnO 2 9.5g of Ag 2 O, 4.5g of carbon-based conductive agent and 15g of activated carbon powder are uniformly mixed and ground for 30min, the particle size of the particles is 100-200nm, and then the particles are dispersed into 400ml of alcohol to prepare slurry, wherein the carbon-based conductive agent is the carbon-based conductive agent in preparation example 1, and the alcohol is 95% alcohol.
S2: to the slurry obtained in step S1 were added 14g of PVDF binder, 1g of sodium sulfate and 6.5g of gas-phase SiO 2 Uniformly mixing to prepare a suspension, carrying out ultrasonic treatment on the suspension for 2min, then pouring and shaping, and carrying out dynamic vacuum drying for 48h at 25 ℃ to obtain the gas-suction precursor.
S3: and immersing the getter precursor into an isopropanol solution of 20% perfluoroheptyl sulfonyl aminoethyl trimethoxysilane, standing at 20 ℃ for 24 hours, taking out the getter precursor, cleaning and drying in vacuum to obtain the composite getter element.
Example 7
A method for manufacturing a composite getter element, comprising the steps of:
s1: 50g of electrolytic MnO 2 10.5g of Ag 2 O, 4.5g of carbon-based conductive agent and 15g of activated carbon powder are uniformly mixed and ground for 30min, the particle size of the particles is 100-200nm, and then the particles are dispersed into 400ml of alcohol to prepare slurry, wherein the carbon-based conductive agent is the carbon-based conductive agent in preparation example 1, and the alcohol is 95% alcohol.
S2: to the slurry obtained in step S1 were added 14g of PVDF binder, 1g of sodium sulfate and 6.5g of gas-phase SiO 2 Uniformly mixing to prepare a suspension, carrying out ultrasonic treatment on the suspension for 3min, then pouring and shaping, and carrying out dynamic vacuum drying for 48h at 25 ℃ to obtain the gas-suction precursor.
S3: and immersing the getter precursor into an isopropanol solution of 20% perfluoroheptyl sulfonyl aminoethyl trimethoxysilane, standing at 20 ℃ for 24 hours, taking out the getter precursor, cleaning and drying in vacuum to obtain the composite getter element.
Example 8
A method for manufacturing a composite getter element, comprising the steps of:
s1: 50g of electrolytic MnO 2 10g of Ag 2 O, 3.5g of carbon-based conductive agent and 15g of activated carbon powder are uniformly mixed and ground for 30min, the particle size of the particles is 100-200nm, and then the particles are dispersed into 400ml of alcohol to prepare slurry, wherein the carbon-based conductive agent is the carbon-based conductive agent in preparation example 1, and the alcohol is 95% alcohol.
S2: to the slurry obtained in step S1 were added 14g of PVDF binder, 3g of sodium sulfate and 5g of gas-phase SiO 2 Uniformly mixing to prepare a suspension, carrying out ultrasonic treatment on the suspension for 3min, then pouring and shaping, and carrying out dynamic vacuum drying for 48h at 25 ℃ to obtain the gas-suction precursor.
S3: and immersing the getter precursor into an isopropanol solution of 20% perfluoroheptyl sulfonyl aminoethyl trimethoxysilane, standing at 25 ℃ for 30 hours, taking out the getter precursor, cleaning and drying in vacuum to obtain the composite getter element.
Example 9
A method for manufacturing a composite getter element, comprising the steps of:
s1: 50g of electrolytic MnO 2 10g of Ag 2 O, 5.5g of carbon-based conductive agent and 15g of activated carbon powder are uniformly mixed and ground for 30min, the particle size of the particles is 100-200nm, and then the particles are dispersed into 400ml of alcohol to prepare slurry, wherein the carbon-based conductive agent is the carbon-based conductive agent in preparation example 1, and the alcohol is 95% alcohol.
S2: to the slurry obtained in step S1 were added 14g of PVDF binder, 3g of sodium sulfate and 8g of gas-phase SiO 2 Uniformly mixing to prepare a suspension, carrying out ultrasonic treatment on the suspension for 3min, then pouring and shaping, and carrying out dynamic vacuum drying for 48h at 25 ℃ to obtain the gas-suction precursor.
S3: and immersing the getter precursor into an isopropanol solution of 20% perfluoroheptyl sulfonyl aminoethyl trimethoxysilane, standing at 25 ℃ for 30 hours, taking out the getter precursor, cleaning and drying in vacuum to obtain the composite getter element.
Example 10
A method for manufacturing a composite getter element, comprising the steps of:
s1: 50g of electrolytic MnO 2 10g of Ag 2 O, 4.5g of carbon-based conductive agent and 15g of activated carbon powder are uniformly mixed and ground for 30min, the particle size of the particles is 100-200nm, and then the particles are dispersed into 400ml of alcohol to prepare slurry, wherein the carbon-based conductive agent is the carbon-based conductive agent in preparation example 1, and the alcohol is 95% alcohol.
S2: to the slurry obtained in step S1 were added 14g of PVDF binder, 1g of sodium sulfate and 5g of gas-phase SiO 2 Uniformly mixing to prepare a suspension, carrying out ultrasonic treatment on the suspension for 3min, then pouring and shaping, and carrying out dynamic vacuum drying for 48h at 25 ℃ to obtain the gas-suction precursor.
S3: and immersing the getter precursor into an isopropanol solution of 20% perfluoroheptyl sulfonyl aminoethyl trimethoxysilane, standing at 25 ℃ for 30 hours, taking out the getter precursor, cleaning and drying in vacuum to obtain the composite getter element.
Example 11
A method for manufacturing a composite getter device, differing from that of example 1 in that Ag powder is used instead of Ag 2 O。
Example 12
A method for manufacturing a composite getter element, which is different from example 1 in that the carbon-based conductive agent of preparation example 2 is used.
Example 13
A method for manufacturing a composite getter element, which is different from example 1 in that the carbon-based conductive agent of preparation example 3 is used.
Example 14
A method for manufacturing a composite getter element, which is different from example 1 in that the carbon-based conductive agent of preparation example 4 is used.
Example 15
A method for producing a composite getter element, which is different from example 1 in that the carbon-based conductive agent of preparation example 5 is used.
Example 16
A method for manufacturing a composite getter element, differing from example 1 in that step S3: immersing the getter precursor into 5% ethanol solution of 3-aminobutyltrimethoxysilane, standing at 40 deg.C for 4h, taking out, cleaning, and vacuum drying. In other embodiments, 3-aminobutyltrimethoxysilane is present in an ethanol solution at a concentration of 3% to 7%.
Example 17
A method for manufacturing a composite getter element, differing from example 16 in that step S3: the dried getter precursor is immersed in a 15% toluene solution of perfluorobutanesulfonyl fluoride again, left at 25 ℃ for 4h, then taken out, washed and dried. In other embodiments, the toluene solution of perfluorobutanesulfonyl fluoride may have a concentration of 10% to 20%.
Example 18
A method for manufacturing a composite getter element, differing from example 1 in that step S3: immersing the gas-absorbing precursor into 5% of vinyl trimethoxy silane ethanol solution, standing at 40 ℃ for 4h, taking out, cleaning and drying; then the precursor is immersed in a toluene solution of 10% of alkene butyl perfluoro (2-isopropyl-1,3-dimethyl-1-butenyl) ether, placed at 25 ℃ for 4h, taken out, cleaned and dried. In other embodiments, the concentration of the ethanolic solution of vinyltrimethoxysilane can range from 3% to 7%; the concentration of the toluene solution of the alkenyl butyl perfluoro (2-isopropyl-1,3-dimethyl-1-butenyl) ether may be 5% to 15%.
Example 19
A method for producing a composite hydrogen absorbing material, which is different from example 1 in that step S3 is not included.
Example 20
The utility model provides a prevent soft packet of lithium cell of flatulence selfreparing, includes electric core, electrolyte and is used for encapsulating the shell of electrolyte, has placed safety element between electric core and the shell, and safety element is formed by the preparation of compound inspiration element. The electrode of the lithium battery can be a lithium metal negative electrode or a negative plate treated by a lithium supplementing process. This example employs a lithium metal negative electrode.
Comparative example
Comparative example 1
Composite suckerThe manufacturing method of the gas member is different from that of example 1 in that Ag in step S1 2 O is 5g.
Comparative example 2
A method for producing a composite hydrogen absorbing material, which is different from that of example 1 in that MnO is electrolyzed in step S1 2 Was 30g.
Comparative example 3
A method for producing a composite hydrogen absorbing material, which is different from that of example 1 in that no carbon-based conductive agent is used in step S1.
Comparative example 4
A method for preparing a composite hydrogen absorbing material, which is different from that of example 1 in that sodium sulfate is not contained in step S2.
Comparative example 5
A pouch lithium battery, which is different from example 20 in that there is no safety element.
Performance test
The composite getter elements manufactured in the respective examples and comparative examples were subjected to a porosity test and a gas absorption capacity test.
The porosity detection method comprises the following steps:
processing a sample into a cylinder with the diameter of 2cm and the height of 2cm, measuring a weight average value m on an analytical balance, and calculating the porosity by a mass-volume method, wherein the calculation formula is as follows:
θ＝(1-m/Vρ s )×100％
in the formula: m is the sample mass (g), V is the sample volume (cm) 3 )，ρ s Is the true density (g/cm) of the sample material 3 )。
The true density is measured by the following steps:
(1) Crushing the sample to be less than 0.15mm, and drying to constant weight;
(2) Weighing 5g of sample, placing the sample in a pycnometer (accurate to 0.2 mg), filling distilled water obtained by rectification into 1/2 of the pycnometer, removing bubbles in water bath for 5min, and cooling to room temperature;
(3) And (3) taking the same distilled water to the position near the scale line of the pycnometer, carrying out water bath for 30min (20 ℃), keeping the liquid level in the bottle to just reach the scale line after the constant temperature is finished, wiping the bottle, and weighing. The true density of the sample is calculated as follows:
ρ s ＝m s ρ/(m s +m 1 -m 2 )
in the formula, m s As the sample mass (g), ρ is the density of distilled water (20 ℃); m is a unit of 1 The mass (g) of the density bottle filled with distilled water; m is 2 The mass (g) is a bottle containing distilled water and a sample density.
The gas absorption capacity detection method comprises the following steps:
weighing a tubular sample having an outer diameter of 2cm, a wall thickness of 0.7mm and a length of 2cm, and recording the weight m of the sample 3 Then placing into a 2L container with a barometer, vacuumizing, and charging N at a rate of 1L/min 2 The inflation time is 3min, the air pressure P at the moment is recorded after the inflation time is kept for 10min 0 Taking out a sample to measure the weight of the sample to be m 4 . The sample is placed into the container again, vacuum pumping is carried out, and then H is filled at the rate of 1L/min 2 、O 2 、CO、CH 2 、C 2 H 4 、CO 2 Mixed gas of (2), H in the mixed gas 2 、O 2 、CO、CH 2 、C 2 H 4 、CO 2 1 1 Then taking out the sample and weighing m 5 . Gas absorption amount is m 5 -m 4 。
The results of the porosity and gettering tests of the materials in each example and comparative example are shown in table 2.
TABLE 2 tables of porosity and gettering capability test data for materials in examples and comparative examples
As can be seen by combining examples 1, 4, 5 and comparative example 2 with Table 2, the ratio of the carbon-based conductive agentAt a certain time, electrolyzing MnO 2 /Ag 2 The ratio of O/active carbon is 5 2 The amount of composite getter element increases and then decreases, when MnO is electrolyzed 2 With Ag 2 When the ratio of O is less than 4.5, for example 3:1, the gettering capability of the composite getter element is greatly reduced.
As can be seen from the combination of examples 3, 6 and 7 and comparative example 1 and Table 2, when the ratio of the carbon-based conductive agent is constant, ag in the raw material for producing the gettering precursor 2 The larger the amount of O added, the higher the gettering ability of the composite gettering member, and MnO can be electrolyzed 2 With Ag 2 The O ratio of 5:1 can achieve better absorption effect, and preferably does not exceed 6:1. When electrolyzing MnO 2 With Ag 2 The proportion of O exceeds 6:1, and the air suction capacity of the composite air suction element is greatly reduced.
It can be seen from the combination of example 1 and comparative example 3 and from table 2 that the getter capacity of the composite getter element is greatly reduced when the carbon-based conductive agent is not present in the raw materials for making the getter precursor. The conductive carbon nano tube and the graphene in the carbon-based conductive agent increase the internal specific surface area of the composite material, and absorbed gas is beneficial to oxidation in later discharge, so that the possibility of gas expansion and swelling of the battery is reduced.
The composite getter elements manufactured in examples 1, 4-5, 11-14, 19 and comparative examples 1-4 were subjected to a conductivity test. The test instrument selects an ST2258C type multifunctional digital four-probe test instrument. The resistivity test results are shown in table 3.
TABLE 3 composite getter element resistivity
As can be seen from Table 3, with MnO 2 With Ag 2 The proportion of O is increased, the resistivity of the composite air suction element is reduced, and the conductivity is obviously improved.
As can be seen from comparison of example 1 with example 19, the electrical conductivity of the surface of the getter precursor was slightly lowered by the water-repellent and oil-repellent treatment, but the overall electrical conductivity remained good.
As can be seen from the data analysis of example 1 and comparative examples 1 and 3, mnO 2 With Ag 2 The proportion of O affects the electrical conductivity of the composite getter element, and the presence or absence of a carbon-based conductive agent has a greater influence on the electrical conductivity of the composite getter element.
The getter elements manufactured in examples 1 and 19 and comparative examples 1 and 3 were applied to lithium batteries of the same batch type, which were divided into four groups, each group having 50 lithium batteries, and the lithium batteries were subjected to charge and discharge experiments, and the average number of charge and discharge of the lithium batteries and the average number of charge and discharge of the batteries when the batteries initially swell were tested and recorded as shown in table 4.
TABLE 4 charging times recording chart for lithium battery charging and discharging times and initial occurrence of bulging
As can be seen from the data in table 4, the composite getter element with hydrophobic and oleophobic treatment can greatly increase the number of times of use of the battery without the occurrence of the gas swelling phenomenon, because of the safety element with hydrophobic and oleophobic properties between the cell body and the housing, and the composite getter element with porous structure that is not blocked by the electrolyte or other liquids can adsorb, store, react and consume gas within the whole life cycle.
Comparative example 3 the composite getter element lacking carbon-based conductive agent is not easily oxidized after gas absorption during charge and discharge due to poor conductivity, which affects the service life of the battery.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A composite getter element is characterized by being prepared from the following raw materials in parts by weight:
electrolytic MnO 2 45-55；
Ag 2 9.5-10.5 of O or Ag;
3.5-5.5% of carbon-based conductive agent;
13-17 parts of activated carbon powder;
13-15 parts of a binder;
1-5 parts of sodium sulfate;
gas phase SiO 2 5-8；
The carbon-based conductive agent is a composition of conductive carbon black, conductive carbon nanotubes and graphene;
the carbon-based conductive agent comprises conductive carbon black: conductive carbon nanotubes: the weight ratio of the graphene is 0.5-1.
2. The composite getter element according to claim 1, wherein: the composite getter element consists of 50 parts by weight of electrolytic MnO 2 10 parts of Ag 2 O or Ag, 4 parts of carbon-based conductive agent, 15 parts of activated carbon powder, 1 part of sodium sulfate, 14 parts of binder and 6 parts of gas-phase SiO 2 And (4) preparing.
3. Composite getter element according to claim 1, wherein the carbon-based conductive agent comprises a conductive carbon black: conductive carbon nanotubes: the weight ratio of graphene is 0.7.
4. Composite getter element according to any of claims 1 to 3, wherein the binder is a polytetrafluoroethylene-based adhesive.
5. A method for the production of a composite getter element as claimed in any of claims 1 to 4, characterized in that it comprises the following steps:
s1: mnO is to be electrolyzed 2 、Ag 2 Mixing O, a carbon-based conductive agent and activated carbon powder uniformly, grinding the mixture to micron level, and dispersing the mixture into a solvent to prepare slurry;
s2: adding a binder, sodium sulfate and gas-phase SiO into the slurry obtained in the step S1 2 Mixing to obtain suspension, and ultrasonic treatingThen pouring and shaping are carried out, dynamic vacuum drying is carried out at room temperature, and a gas suction precursor is obtained after cooling;
s3: and (3) performing surface hydrophobic and oleophobic treatment on the gas absorption precursor in the step (S2) to obtain the composite gas absorption element.
6. The preparation method of the composite getter element according to claim 5, wherein in the step S3, the hydrophobic and oleophobic treatment is to impregnate at least one of an organic fluorine-containing material, an organic silicon material or an organic fluorine-silicon material on the surface of the getter precursor, the surface treatment temperature is 25-50 ℃, and the temperature is kept for 3-24h.
7. A method for preparing a composite getter element according to claim 6, wherein the hydrophobic and oleophobic treatments are: immersing the air-breathing precursor into an isopropanol solution of 18-22% perfluoroheptyl sulfonyl aminoethyl trimethoxysilane, standing at 25 ℃ for 24 hours, taking out, cleaning and drying;
or immersing the air-breathing precursor into 3-7% of ethanol solution of 3-aminobutyltrimethoxysilane, standing at 40 ℃ for 4h, taking out, cleaning and drying;
or immersing the gas-absorbing precursor into 3-7% of ethanol solution of vinyl trimethoxy silane, standing at 40 ℃ for 4h, taking out, cleaning and drying; then the precursor is immersed in a toluene solution of 5% -15% of alkene butyl perfluoro (2-isopropyl-1,3-dimethyl-1-butenyl) ether, placed at 25 ℃ for 4h, taken out, cleaned and dried.
8. The method for manufacturing a composite getter element according to claim 7, wherein the hydrophobic and oleophobic treatment further comprises: and taking out the gas absorption precursor from the ethanol solution of 3-aminobutyltrimethoxysilane, drying, soaking the dried gas absorption precursor into 10-20% of toluene solution of perfluorobutylsulfonyl fluoride, standing at 25 ℃ for 4h, taking out, cleaning and drying.
9. An anti-flatulence self-repairing soft package lithium battery, which comprises an electric core, an electrolyte and a shell for packaging the electrolyte, and is characterized by further comprising a safety element manufactured by the composite air suction element in any one of claims 1 to 8, wherein the safety element is positioned between the electric core and the shell.
10. The flatulence-preventing and self-repairing soft-package lithium battery of claim 9, wherein the negative electrode of the lithium battery is a lithium metal negative electrode or a negative electrode sheet processed by a lithium supplement process.
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