CN115473008A - Lithium-supplement type isolation film, battery cell and secondary battery - Google Patents
Lithium-supplement type isolation film, battery cell and secondary battery Download PDFInfo
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- CN115473008A CN115473008A CN202211193242.8A CN202211193242A CN115473008A CN 115473008 A CN115473008 A CN 115473008A CN 202211193242 A CN202211193242 A CN 202211193242A CN 115473008 A CN115473008 A CN 115473008A
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- 239000013589 supplement Substances 0.000 title claims abstract description 136
- 238000002955 isolation Methods 0.000 title claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 150
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 150
- 239000000654 additive Substances 0.000 claims abstract description 79
- 230000000996 additive effect Effects 0.000 claims abstract description 78
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- 238000000926 separation method Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
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- 229910018068 Li 2 O Inorganic materials 0.000 claims description 7
- 229910018071 Li 2 O 2 Inorganic materials 0.000 claims description 7
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
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- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
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- 235000019322 gelatine Nutrition 0.000 claims description 3
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- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000002322 conducting polymer Substances 0.000 claims 1
- 239000013543 active substance Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 8
- 238000013461 design Methods 0.000 description 6
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
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- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a lithium-supplementing type isolating membrane, a battery cell and a secondary battery, which comprise an isolating membrane body, a porous conducting film and mixed slurry of a sacrificial lithium-supplementing additive; wherein, the two opposite surfaces of the porous conductive film are respectively provided with the isolating film body; the mixed slurry of the sacrificial lithium supplement additive is coated on at least one of the two opposite surfaces of the porous conductive film and is positioned between the porous conductive film and the isolation film body. The invention can ensure sufficient supply of active lithium, can avoid the damage to the structure of the positive pole piece after the mixed slurry of the sacrificial lithium supplement additive is decomposed to generate gas, and meanwhile, the porous conductive film can improve the conductivity of the mixed slurry of the sacrificial lithium supplement additive, and can not influence the proportion of active substances in the positive pole piece, thereby not reducing the energy density of the battery, and being suitable for large-scale popularization and application.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a lithium-supplement type isolation film, a battery core and a secondary battery.
Background
With the rapid development of electric vehicles, lithium ion batteries are one of the most important components of electric vehicles, and the position of the lithium ion batteries is increasingly prominent, so that the development space is huge.
In the past, the pursuit of lithium ion batteries in the electric automobile industry is to achieve both high energy density and long cycle performance, and to achieve this performance goal, lithium supplement technology has been proposed and receives widespread social attention. The effect of lithium supplement of the negative electrode is most obvious, but the activity of the lithium powder is very high, so that very high requirements on the safety production of the lithium ion battery are provided, and meanwhile, new equipment is required to be introduced, so that the production investment is increased; compared with the positive electrode lithium supplement, the positive electrode lithium supplement material has lower sensitivity to the environment than a pure lithium belt and lithium powder, is safer, and can be directly added in the positive electrode homogenizing process, so that new equipment does not need to be added, the process does not need to be adjusted, the positive electrode lithium supplement material can be more quickly adapted to the existing production line, and the batch application can be more quickly realized.
At present, three types of anode lithium supplement materials are commonly used in the market, the first type is a lithium-rich compound, such as lithium-rich lithium nickelate (Li 2NiO 2) and lithium-rich lithium ferrite (Li 5FeO 4); the second is a reverse-conversion nanocomposite, such as Co/Li 2 O、Fe/Li 2 O and Mn/Li 2 O; the third is a sacrificial positive electrode lithium supplement additive, such as Li 2 O 2 ，Li 2 O，LiN 3 ，Li 2 C 2 O 4 ，Li 2 C 4 O 4 . After the sacrificial positive electrode lithium supplement additive is mixed with a positive electrode material and homogenized to be manufactured into a battery, the sacrificial positive electrode lithium supplement additive is decomposed in a charging stage, li in the sacrificial positive electrode lithium supplement additive can be inserted into a negative electrode, and other components can be exhausted in a gas form through air exhaust. The sacrificial anode lithium supplement additive has high lithium supplement capacity, does not remain, and does not influence the performance of the anode main material, so that the sacrificial anode lithium supplement additive receives more attention and research than other two anode lithium supplement materials. However,the positive electrode lithium-supplementing material also has some practical problems, such as: (1) After the lithium ion battery is charged to a decomposition voltage, the sacrificial anode lithium supplement additive can be completely decomposed, so that holes can be formed in an anode piece, a conductive network of an anode material is influenced, an electronic migration path is incomplete, and the performance of the battery is reduced; (2) The anode material needs to be added with a conductive agent in a large proportion to fully exert the capacity of the sacrificial anode lithium supplement additive, and the proportion of active substances is reduced by the anode material, so that the energy density of the battery is reduced.
Therefore, improvements in the prior art are needed.
The above information is given as background information only to aid in understanding the present disclosure, and no determination or admission is made as to whether any of the above is available as prior art against the present disclosure.
Disclosure of Invention
The invention provides a lithium-supplementing type isolation film, a battery cell and a secondary battery, so as to solve the defects of the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
in a first aspect, the invention provides a lithium-supplement type isolation film, which comprises an isolation film body 1, a porous conductive film 2 and a mixed slurry 3 of a sacrificial lithium-supplement additive; wherein the content of the first and second substances,
the two opposite surfaces of the porous conductive film 2 are respectively provided with the isolating film body 1;
the mixed slurry 3 of the sacrificial lithium supplement additive is coated on at least one of the two opposite surfaces of the porous conductive film 2 and is positioned between the porous conductive film 2 and the separation film body 1.
In the lithium-supplement type separator, a positive electrode lithium-supplement electrode tab 4 is formed by die cutting the part of the porous conductive film 2 exposed out of the separator body 1.
Further, in the lithium supplement type separator, the mixed slurry 3 of the sacrificial lithium supplement additive comprises a lithium-containing compound, a conductive agent and a binder;
the conductive agent is wrapped on the surface of the lithium-containing compound.
Further, in the lithium supplement type isolation film, the percentage of the lithium-containing compound in the mixed slurry 3 of the sacrificial lithium supplement additive is 0-50%;
the conductive agent accounts for 50-70% of the total weight of the mixed slurry 3 of the sacrificial lithium supplement additive;
the adhesive accounts for 1-5% of the total weight of the mixed slurry 3 of the sacrificial lithium supplement additive.
Further, in the lithium-supplement type separator, the lithium-containing compound is Li 2 O 2 、Li 2 O、LiN 3 、Li 2 C 2 O 4 、Li 2 C 4 O 4 At least one of;
the conductive agent is at least one of conductive carbon black, conductive graphite, conductive carbon nanotubes and conductive graphene;
the binder is at least one of polyacrylate, polyethylene oxide, rubber, polyurethane, sodium carboxymethylcellulose, polyacrylic acid, gelatin and chitosan.
Further, in the lithium supplement type isolation film, the thickness of the isolation film body 1 is 3.0-20um;
the thickness of the porous conductive film 2 is 1.0-50um;
the coating thickness of the mixed slurry 3 of the sacrificial lithium supplement additive is 1.0-10um.
In the lithium-supplement type isolation film, the isolation film body 1 is made of a high molecular compound;
the porous conductive film 2 is made of a conductive polymer compound.
In a second aspect, the present invention provides a battery cell, including a negative electrode plate, a positive electrode plate, and a separator disposed between the positive electrode plate and the negative electrode plate, where the separator is the lithium-supplement separator described in the first aspect.
Further, in the battery cell, when the positive electrode is used for supplementing lithium, the positive electrode lithium supplementing pole tab 4 in the lithium supplementing type isolating membrane is connected with the negative pole tab 5 in the negative pole piece through an external power supply.
Furthermore, in the battery cell, a positive electrode lithium supplement pole lug (4) in the lithium supplement type isolating membrane is connected with an external lithium supplement pole column;
and the external power supply is connected with the external lithium-supplement pole and the negative pole.
Further, in the battery cell, when the voltage reaches the decomposition voltage of the sacrificial lithium supplement additive, li in the sacrificial lithium supplement additive is embedded into the negative electrode, and gas is released at the same time to supplement lithium; the charging current is 0.005C-0.2C, wherein C is the rated capacity of the sacrificial lithium supplement additive.
In a third aspect, the present invention provides a secondary battery, including a battery cell and a casing accommodating the battery cell, where the battery cell is the battery cell according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the lithium supplement type isolating membrane, the battery cell and the secondary battery provided by the embodiment of the invention, the mixed slurry of the sacrificial type lithium supplement additive is wrapped in the isolating membrane body and coated on the surface of the porous conducting film so as to separate the mixed slurry of the sacrificial type lithium supplement additive from the positive active material, so that sufficient supplement of active lithium can be ensured, the phenomenon that the mixed slurry of the sacrificial type lithium supplement additive decomposes to generate gas and then damages the structure of a positive pole piece can be avoided, meanwhile, the porous conducting film can improve the conductivity of the mixed slurry of the sacrificial type lithium supplement additive, the proportion of the active material in the positive pole piece can not be influenced, the energy density of the battery can not be reduced, and the lithium supplement type isolating membrane, the battery cell and the secondary battery are suitable for large-scale popularization and application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural side view of a lithium-doped separator according to an embodiment of the present invention;
FIG. 2 is a schematic diagram illustrating a side view of a lithium-doped barrier film according to an embodiment of the present invention;
FIG. 3 is a schematic top view of a lithium-doped separator according to an embodiment of the present invention;
fig. 4 is a schematic top view of a structure of a battery cell according to a second embodiment of the present invention.
Reference numerals are as follows:
the lithium ion battery comprises a separation film body 1, a porous conductive film 2, mixed slurry 3 of a sacrificial lithium supplement additive, a positive electrode lithium supplement electrode lug 4, a negative electrode lug 5 and a positive electrode lug 6.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the description of the present invention, it is to be understood that when an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. When a component is referred to as being "disposed on" another component, it can be directly on the other component or intervening components may also be present.
Furthermore, the terms "long", "short", "inner", "outer", and the like indicate orientations or positional relationships based on orientations or positional relationships illustrated in the drawings, and are merely for convenience of description of the present invention, but do not indicate or imply that the device or element referred to must have the specific orientation, be configured to operate in the specific orientation, and thus, should not be construed as limiting the present invention.
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example one
In view of the above-mentioned defects of the conventional lithium supplementing technology for batteries, the applicant of the present invention is based on the practical experience and professional knowledge that are abundant for many years in the design and manufacture of such products, and is actively researched and innovated in cooperation with the application of the theory, so as to hopefully create a technology capable of solving the defects in the prior art, and make the lithium supplementing technology for batteries more practical. After continuous research and design and repeated trial production and improvement, the invention with practical value is finally created.
Referring to fig. 1-2, an embodiment of the invention provides a lithium-supplement type separator, which includes a separator body 1, a porous conductive film 2, and a mixed slurry 3 of a sacrificial lithium-supplement additive; wherein the content of the first and second substances,
the two opposite surfaces of the porous conductive film 2 are respectively provided with the isolating film body 1;
the mixed slurry 3 of the sacrificial lithium supplement additive is coated on at least one of the two opposite surfaces of the porous conductive film 2 and is positioned between the porous conductive film 2 and the separation film body 1. Fig. 1 shows a case where the mixed paste 3 of the sacrificial lithium supplement additive is coated on one surface of the porous conductive film 2, and fig. 2 shows a case where the mixed paste 3 of the sacrificial lithium supplement additive is coated on both opposite surfaces of the porous conductive film 2.
In this embodiment, although the sacrificial lithium supplement additive is also added to the lithium ion battery, unlike the prior art in which the sacrificial lithium supplement additive is directly mixed with the positive electrode material to form the positive electrode slurry and the positive electrode sheet is made, in this embodiment, the sacrificial lithium supplement additive is not used as a part of the positive electrode sheet, but used as a part of the separator. Specifically, the original separator only includes the separator body 1, and the separator provided in this embodiment includes the sacrificial lithium supplement additive mixed slurry 3 and the porous conductive film 2 in addition to the separator body 1. The sacrificial lithium supplement additive mixed slurry 3 is wrapped in the isolating membrane body 1 and coated on the surface of the porous conducting membrane 2 (the sacrificial lithium supplement additive mixed slurry can be connected with an external circuit through the porous conducting membrane 2), so that the sacrificial lithium supplement additive mixed slurry 3 is separated from the positive electrode material, the structure of the positive electrode plate cannot be damaged even if the sacrificial lithium supplement additive mixed slurry 3 is decomposed to supplement lithium and then generates gas, namely, holes cannot be formed in the positive electrode plate, the completeness of the migration path of electrons can be guaranteed, the performance of the battery can be guaranteed, meanwhile, the sacrificial lithium supplement additive is extremely high in resistance and poor in conductivity, the porous conducting membrane 2 provided by the embodiment can improve the conductivity of the sacrificial lithium supplement additive, and as the conductive agent with a large proportion does not need to be added into the positive electrode material, the proportion of active substances in the positive electrode plate cannot be influenced, and the energy density of the battery cannot be reduced.
Referring to fig. 3, in the present embodiment, a portion of the porous conductive film 2 exposed to the separator body 1 is die-cut to form a positive electrode lithium supplement electrode tab 4.
It should be noted that the height of the porous conductive film 2 provided in this embodiment is higher than that of the separator body 1, that is, a part of the porous conductive film 2 is exposed out of the separator body 1, and this part needs to form a positive electrode lithium supplement electrode tab 4 that can be connected to an external lithium supplement electrode column by die cutting.
In this embodiment, the mixed slurry 3 of the sacrificial lithium supplement additive includes a lithium-containing compound, a conductive agent, and a binder;
the conductive agent is wrapped on the surface of the lithium-containing compound.
In addition, in this embodiment, the conductive agent is wrapped on the surface of the lithium-containing compound, so that the conductivity of the positive electrode lithium supplement additive is further improved.
In this embodiment, the percentage of the lithium-containing compound to the total weight of the mixed slurry 3 of the sacrificial lithium supplement additive is 0% to 50%;
the conductive agent accounts for 50-70% of the total weight of the mixed slurry 3 of the sacrificial lithium supplement additive;
the adhesive accounts for 1-5% of the total weight of the mixed slurry 3 of the sacrificial lithium supplement additive.
In the mixed slurry 3 of the sacrificial lithium supplement additive, the ratio of the lithium-containing compound, the conductive agent and the binder needs to be reasonably matched, and the lithium supplement effect may be affected by too little or too much of any of the substances.
In this embodiment, the lithium-containing compound is Li 2 O 2 、Li 2 O、LiN 3 、Li 2 C 2 O 4 、Li 2 C 4 O 4 At least one of;
of course, the lithium-containing compound may also be another compound composed of lithium and other elements, as long as the composed compound can take off Li during charging and release gas.
The conductive agent is at least one of conductive carbon black, conductive graphite, conductive carbon nanotubes and conductive graphene;
the binder is at least one of polyacrylate, polyethylene oxide, rubber, polyurethane, sodium carboxymethylcellulose, polyacrylic acid, gelatin and chitosan.
Similarly, the conductive agent and the binder may also be other substances, which are not listed in this embodiment.
In this embodiment, the thickness of the isolation film body 1 is 3.0-20um;
the thickness of the porous conductive film 2 is 1.0-50um;
the coating thickness of the mixed slurry 3 of the sacrificial lithium supplement additive is 1.0-10um.
The thickness values can be adjusted according to the actually required lithium supplement amount.
In this embodiment, the isolation film body 1 is a common isolation film, and is made of a high molecular compound, such as polypropylene, polyethylene, etc.;
the porous conductive film 2 is made of a conductive polymer compound, such as conductive carbon-doped polypropylene, conductive carbon-doped polyethylene, or the like.
Illustratively, two 5um polyethylene-made barrier film bodies 1 and one 5um conductive carbon-doped polyethylene-made porous conductive film 2 may be selected, and the sacrificial lithium supplement additive mixed slurry 3 (Li) is coated on the porous conductive film 2 2 O 2 ) And then stacking to form the lithium-supplement type isolation film.
To verify the feasibility of the scheme provided in this example, the following experiment was performed:
with sacrificial Li 2 O 2 Materials are taken as examples; selecting a 7um Polyethylene (PE) diaphragm as a diaphragm body, and selecting a 2um thick conductive carbon-doped polypropylene polymer conductive film as a carrier of the sacrificial lithium supplement additive slurry; sacrificial Li 2 O 2 The coating thickness of the material is 2um and 5um; wherein Li 2 O 2 The theoretical gram capacity of the material is 1168mAh/g, but the material has poor environmental stability and is very easy to be mixed with H in air 2 O and CO 2 React to form LiOH and Li 2 CO 3 At present, the stable and exerted capacity of the sacrificial lithium supplement material is about 900mAh/g; the capacity performance of the lithium supplement additive after the battery was produced is shown in table 1 below;
table 1: capacity exertion of lithium supplement additive
As can be seen from Table 1, li was added due to the lithium supplement 2 O 2 The self powder has extremely high impedance, the material polarization is large with large multiplying power (after being more than 0.2C), the charging process quickly reaches the material decomposition potential, and the decomposition cut-off condition is triggered, so that the material is not completely decomposed; as above, when chargingWhen the electric multiplying power reaches 0.5C, the capacity exertion of the lithium supplement additive is reduced by about 50mAh/g.
Although the terms separator bulk, porous conductive film, mixed slurry of sacrificial lithium supplement additives, positive electrode lithium supplement electrode tab, etc. are used more often herein, the possibility of using other terms is not excluded. These terms are used merely to more conveniently describe and explain the nature of the present invention; they are to be construed as being without limitation to any additional limitations that may be imposed by the spirit of the present invention.
According to the lithium supplement type isolating membrane provided by the embodiment of the invention, the mixed slurry of the sacrificial lithium supplement additive is wrapped in the isolating membrane body and coated on the surface of the porous conducting membrane so as to separate the mixed slurry of the sacrificial lithium supplement additive from the positive active material, so that sufficient supplement of active lithium can be ensured, the phenomenon that the mixed slurry of the sacrificial lithium supplement additive decomposes to generate gas and then damages the structure of a positive pole piece can be avoided, meanwhile, the porous conducting membrane can improve the conductivity of the mixed slurry of the sacrificial lithium supplement additive, the proportion of the active material in the positive pole piece cannot be influenced, the energy density of a battery cannot be reduced, and the lithium supplement type isolating membrane is suitable for large-scale popularization and application.
Example two
Referring to fig. 4, an embodiment of the invention provides a battery cell, including a negative electrode plate, a positive electrode plate, and a separation film disposed between the positive electrode plate and the negative electrode plate, where the separation film is the lithium-supplement separation film according to the first embodiment.
It should be noted that, this embodiment is only to improve the isolation film, and the positive electrode plate and the negative electrode plate are still consistent with those in the conventional technology, and in view of that these designs have been implemented in the prior art and are not the key points of the design of this scheme, no further explanation is made here.
In this embodiment, the battery cell is formed by any one of stacking, winding, stacking and winding the positive electrode plate, the separator, and the negative electrode plate.
After the cell structure is assembled, an external power supply can be used for connecting a positive electrode lithium supplement electrode tab 4 in the lithium supplement type isolating membrane with a negative electrode tab 5 in the negative electrode plate, when the voltage reaches the decomposition voltage of the positive electrode lithium supplement additive, li in the positive electrode lithium supplement additive is embedded into the negative electrode, and meanwhile, gas is released, so that lithium supplement is realized; wherein the charging current is 0.005C-0.2C, and C is the rated capacity of the lithium supplement additive of the anode; then, a negative electrode tab 5 and a positive electrode tab 6 are connected, and the activity and the capacity grading are carried out according to the conventional lithium ion battery.
According to the battery cell provided by the embodiment of the invention, the mixed slurry of the sacrificial lithium supplement additive is wrapped in the isolating membrane body and coated on the surface of the porous conducting membrane so as to separate the mixed slurry of the sacrificial lithium supplement additive from the positive active material, so that sufficient supply of active lithium can be ensured, the problem that the mixed slurry of the sacrificial lithium supplement additive is decomposed to generate gas and then the structure of a positive pole piece is damaged can be avoided, meanwhile, the porous conducting membrane can improve the conductivity of the mixed slurry of the sacrificial lithium supplement additive, the active material proportion in the positive pole piece is not influenced, the energy density of the battery is not reduced, and the battery cell is suitable for large-scale popularization and application.
EXAMPLE III
The invention provides a secondary battery, which comprises a battery cell and a shell for accommodating the battery cell, wherein the battery cell is the battery cell described in the second embodiment.
It should be noted that the secondary battery further includes necessary component designs such as an electrolyte and a top cap, and the specific functions of these component designs are to ensure that each function of the secondary battery works normally.
In addition, the secondary battery in the present embodiment may be applied to, but not limited to, electronic devices such as electronic devices, electric vehicles, or power storage systems. The electronic device may be, for example, various computers, mobile phones, display panels, and the like, which use a secondary battery as a driving power source. The electric vehicle may be, for example, an electric vehicle, an electric tricycle, an electric bicycle, or the like that uses a secondary battery as a driving power source. The electric power storage system may be, for example, an electric power storage system that uses a secondary battery as an electric power storage source.
In these electronic devices, the secondary battery may be electrically connected to the electric element to supply electric power to the electric element. Because the rapid charging ability of the secondary battery provided by the application is excellent, the electronic equipment is favorably used in application scenes such as outdoor energy storage, short-time power supply, mobile energy storage and the like, so that the application scenes of the electronic equipment are wider.
According to the secondary battery provided by the embodiment of the invention, the mixed slurry of the sacrificial lithium supplement additive is wrapped in the isolating membrane body and coated on the surface of the porous conducting membrane so as to separate the mixed slurry of the sacrificial lithium supplement additive from the positive active material, so that sufficient supply of active lithium can be ensured, the problem that the mixed slurry of the sacrificial lithium supplement additive is decomposed to generate gas and then the structure of a positive pole piece is damaged can be avoided, meanwhile, the porous conducting membrane can improve the conductivity of the mixed slurry of the sacrificial lithium supplement additive, the active material proportion in the positive pole piece is not influenced, the energy density of the battery is not reduced, and the secondary battery is suitable for large-scale popularization and application.
In conclusion, upon reading the present detailed disclosure, those skilled in the art will appreciate that the foregoing detailed disclosure can be presented by way of example only, and not limitation. Those skilled in the art will appreciate that the present application is intended to cover various reasonable variations, adaptations, and modifications of the embodiments described herein, although not explicitly described herein. Such alterations, improvements, and modifications are intended to be suggested by this application and are within the spirit and scope of the exemplary embodiments of the application.
Furthermore, certain terminology has been used in this application to describe embodiments of the application. For example, "one embodiment," "an embodiment," and/or "some embodiments" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the present application. Therefore, it is emphasized and should be appreciated that two or more references to "an embodiment" or "one embodiment" or "an alternative embodiment" in various portions of this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined as suitable in one or more embodiments of the application.
It should be appreciated that in the foregoing description of embodiments of the present application, various features are grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure aiding in the understanding of one feature. This is not to be taken as an admission that any of the features of the claims are essential, and it is fully possible for a person skilled in the art to extract some of them as separate embodiments when reading the present application. That is, embodiments in the present application may also be understood as an integration of multiple sub-embodiments. And each sub-embodiment described herein is equally applicable in less than all features of a single foregoing disclosed embodiment.
Each patent, patent application, publication of a patent application, and other material, such as articles, books, descriptions, publications, documents, articles, and the like, cited herein is hereby incorporated by reference. All matters hithertofore set forth herein except as related to any prosecution history, may be inconsistent or conflicting with this document or any prosecution history which may have a limiting effect on the broadest scope of the claims. Now or later associated with this document. For example, if there is any inconsistency or conflict in the description, definition, and/or use of terms associated with any of the included materials with respect to the terms, descriptions, definitions, and/or uses associated with this document, the terms in this document are used.
Finally, it should be understood that the embodiments of the application disclosed herein are illustrative of the principles of the embodiments of the present application. Other modified embodiments are also within the scope of the present application. Accordingly, the disclosed embodiments are presented by way of example only, and not limitation. Those skilled in the art can implement the present application in alternative configurations according to the embodiments of the present application. Thus, embodiments of the present application are not limited to those precisely described in the application.
Claims (12)
1. The lithium supplement type isolation membrane is characterized by comprising an isolation membrane body (1), a porous conductive membrane (2) and mixed slurry (3) of a sacrificial lithium supplement additive; wherein the content of the first and second substances,
the two opposite surfaces of the porous conductive film (2) are respectively provided with the isolating film body (1);
the mixed slurry (3) of the sacrificial lithium supplement additive is coated on at least one of two opposite surfaces of the porous conductive film (2) and is positioned between the porous conductive film (2) and the isolation film body (1).
2. The lithium supplement type separator according to claim 1, wherein the part of the porous conductive film (2) exposed to the separator body (1) is die-cut to form a positive electrode lithium supplement electrode tab (4).
3. The lithium-supplementing separator according to claim 1, wherein the mixed slurry (3) of the sacrificial lithium-supplementing additive comprises a lithium-containing compound, a conductive agent, and a binder;
the conductive agent is wrapped on the surface of the lithium-containing compound.
4. The lithium-supplementing type separator according to claim 3, wherein the percentage of the lithium-containing compound to the total weight of the mixed slurry (3) of the sacrificial lithium-supplementing additive is 0% to 50%;
the conductive agent accounts for 50-70% of the total weight of the mixed slurry (3) of the sacrificial lithium supplement additive;
the adhesive accounts for 1-5% of the total weight of the mixed slurry (3) of the sacrificial lithium supplement additive.
5. The lithium-supplement type separator according to claim 3, wherein the lithium-containing compound is Li 2 O 2 、Li 2 O、LiN 3 、Li 2 C 2 O 4 、Li 2 C 4 O 4 At least one of;
the conductive agent is at least one of conductive carbon black, conductive graphite, conductive carbon nanotubes and conductive graphene;
the binder is at least one of polyacrylate, polyethylene oxide, rubber, polyurethane, sodium carboxymethylcellulose, polyacrylic acid, gelatin and chitosan.
6. The separator of claim 1, wherein the separator body (1) has a thickness of 3.0-20um;
the thickness of the porous conductive film (2) is 1.0-50um;
the coating thickness of the mixed slurry (3) of the sacrificial lithium supplement additive is 1.0-10um.
7. The lithium-supplement separator according to claim 1, wherein the separator body (1) is made of a polymer compound;
the material of the porous conducting film (2) is a conducting polymer compound.
8. An electric core, comprising a negative pole piece, a positive pole piece and a separation film arranged between the positive pole piece and the negative pole piece, wherein the separation film is the lithium-supplementing separation film according to any one of claims 1 to 7.
9. The battery core according to claim 8, wherein when the positive electrode lithium supplement is performed, a positive electrode lithium supplement electrode tab (4) in the lithium supplement type separation film is connected with a negative electrode tab (5) in the negative electrode piece through an external power supply.
10. The battery cell of claim 9, wherein the positive lithium supplement electrode tab (4) in the lithium supplement type separator is connected with an external lithium supplement electrode column;
and the external power supply is connected with the external lithium supplement pole and the negative pole.
11. The battery cell of claim 9, wherein when the voltage reaches the decomposition voltage of the sacrificial lithium supplement additive, li in the sacrificial lithium supplement additive is inserted into the negative electrode, and gas is released to supplement lithium; the charging current is 0.005C-0.2C, wherein C is the rated capacity of the sacrificial lithium supplement additive.
12. A secondary battery comprising a cell and a casing housing the cell, wherein the cell is a cell according to any of claims 8 to 11.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103650203A (en) * | 2011-07-07 | 2014-03-19 | 丰田自动车株式会社 | Secondary battery |
| CN106684298A (en) * | 2017-01-22 | 2017-05-17 | 湖南立方新能源科技有限责任公司 | Lithium-ion battery separator and application thereof |
| CN107845829A (en) * | 2017-10-12 | 2018-03-27 | 北京卫蓝新能源科技有限公司 | A kind of two-layer compound diaphragm cell and its benefit lithium method |
| CN109546063A (en) * | 2018-12-13 | 2019-03-29 | 许昌学院 | A kind of compound diaphragm for lithium ion battery |
| CN109616603A (en) * | 2018-12-05 | 2019-04-12 | 清华大学深圳研究生院 | Diaphragm, diaphragm preparation method and application diaphragm device |
| CN109755448A (en) * | 2018-12-28 | 2019-05-14 | 北京中能东道绿驰科技有限公司 | A kind of lithium battery diaphragm and preparation method thereof with benefit lithium coating |
| CN110571391A (en) * | 2018-06-05 | 2019-12-13 | 湖北猛狮新能源科技有限公司 | Preparation method of lithium-supplement composite diaphragm |
| CN111384428A (en) * | 2018-12-29 | 2020-07-07 | 宁德时代新能源科技股份有限公司 | Lithium supplement agent, positive pole piece, isolating membrane and lithium ion battery |
| CN112038554A (en) * | 2020-10-14 | 2020-12-04 | 昆山宝创新能源科技有限公司 | Composite diaphragm and application thereof |
| CN113078417A (en) * | 2021-03-12 | 2021-07-06 | 天津市捷威动力工业有限公司 | Composite lithium-supplementing diaphragm and secondary battery thereof |
| CN216528955U (en) * | 2021-10-29 | 2022-05-13 | 东莞市创明电池技术有限公司 | Lithium reference electrode and three-electrode lithium ion battery |
| WO2022117080A1 (en) * | 2020-12-04 | 2022-06-09 | 比亚迪股份有限公司 | Lithium ion battery and power vehicle |
| WO2022156383A1 (en) * | 2021-01-25 | 2022-07-28 | 上海汉行科技有限公司 | Storage battery capable of being continuously supplemented lithium/sodium |
-
2022
- 2022-09-28 CN CN202211193242.8A patent/CN115473008B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103650203A (en) * | 2011-07-07 | 2014-03-19 | 丰田自动车株式会社 | Secondary battery |
| CN106684298A (en) * | 2017-01-22 | 2017-05-17 | 湖南立方新能源科技有限责任公司 | Lithium-ion battery separator and application thereof |
| CN107845829A (en) * | 2017-10-12 | 2018-03-27 | 北京卫蓝新能源科技有限公司 | A kind of two-layer compound diaphragm cell and its benefit lithium method |
| CN110571391A (en) * | 2018-06-05 | 2019-12-13 | 湖北猛狮新能源科技有限公司 | Preparation method of lithium-supplement composite diaphragm |
| CN109616603A (en) * | 2018-12-05 | 2019-04-12 | 清华大学深圳研究生院 | Diaphragm, diaphragm preparation method and application diaphragm device |
| CN109546063A (en) * | 2018-12-13 | 2019-03-29 | 许昌学院 | A kind of compound diaphragm for lithium ion battery |
| CN109755448A (en) * | 2018-12-28 | 2019-05-14 | 北京中能东道绿驰科技有限公司 | A kind of lithium battery diaphragm and preparation method thereof with benefit lithium coating |
| CN111384428A (en) * | 2018-12-29 | 2020-07-07 | 宁德时代新能源科技股份有限公司 | Lithium supplement agent, positive pole piece, isolating membrane and lithium ion battery |
| CN112038554A (en) * | 2020-10-14 | 2020-12-04 | 昆山宝创新能源科技有限公司 | Composite diaphragm and application thereof |
| WO2022117080A1 (en) * | 2020-12-04 | 2022-06-09 | 比亚迪股份有限公司 | Lithium ion battery and power vehicle |
| WO2022156383A1 (en) * | 2021-01-25 | 2022-07-28 | 上海汉行科技有限公司 | Storage battery capable of being continuously supplemented lithium/sodium |
| CN113078417A (en) * | 2021-03-12 | 2021-07-06 | 天津市捷威动力工业有限公司 | Composite lithium-supplementing diaphragm and secondary battery thereof |
| WO2022188355A1 (en) * | 2021-03-12 | 2022-09-15 | 天津市捷威动力工业有限公司 | Composite lithium compensation diaphragm and secondary battery comprising same |
| CN216528955U (en) * | 2021-10-29 | 2022-05-13 | 东莞市创明电池技术有限公司 | Lithium reference electrode and three-electrode lithium ion battery |
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|---|---|
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