CN114050308A - Negative-electrode-free lithium battery structure and preparation method of negative-electrode-free lithium battery - Google Patents
Negative-electrode-free lithium battery structure and preparation method of negative-electrode-free lithium battery Download PDFInfo
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- CN114050308A CN114050308A CN202111129015.4A CN202111129015A CN114050308A CN 114050308 A CN114050308 A CN 114050308A CN 202111129015 A CN202111129015 A CN 202111129015A CN 114050308 A CN114050308 A CN 114050308A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 239000011889 copper foil Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000002000 Electrolyte additive Substances 0.000 claims description 9
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
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- 239000000956 alloy Substances 0.000 claims description 6
- 238000005524 ceramic coating Methods 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- HBTFAPFDKZZJDM-UHFFFAOYSA-N [O-]B(OC(C(C(F)(F)F)(C(F)(F)F)C1(C(C2(F)F)(F)F)F)(C1(F)F)C2(C(F)(F)F)F)OC(C(C(F)(F)F)(C(F)(F)F)C1(C(C2(F)F)(F)F)F)(C1(F)F)C2(C(F)(F)F)F.[Li+] Chemical compound [O-]B(OC(C(C(F)(F)F)(C(F)(F)F)C1(C(C2(F)F)(F)F)F)(C1(F)F)C2(C(F)(F)F)F)OC(C(C(F)(F)F)(C(F)(F)F)C1(C(C2(F)F)(F)F)F)(C1(F)F)C2(C(F)(F)F)F.[Li+] HBTFAPFDKZZJDM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 238000009713 electroplating Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 3
- -1 lithium nickel aluminum cobalt oxide Chemical compound 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 3
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 claims description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 150000002641 lithium Chemical class 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 3
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- 230000001939 inductive effect Effects 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
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- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to the technical field of lithium batteries, in particular to a structure of a lithium battery without a negative electrode and a preparation method of the lithium battery without the negative electrode. The structure of the non-negative lithium battery comprises a positive current collector and a negative current collector, wherein a cathode lithium source coating is arranged outside the positive current collector, a liquid metal coating is arranged outside the negative current collector, and the positive current collector and the negative current collector are separated by a diaphragm which is mutually attached with the positive current collector and the negative current collector. The manufacturing method comprises the following steps: and assembling the positive electrode material, the structure of the non-negative lithium battery and the electrolyte together to obtain the non-negative lithium battery. The advantages are that: the problem that the energy density of the existing lithium battery is insufficient is solved, and the energy density is effectively improved.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a structure of a lithium battery without a negative electrode and a preparation method of the lithium battery without the negative electrode.
Background
At present, the traditional lithium ion battery cannot meet the requirements of various emerging fields on the energy density of the lithium battery. Therefore, the non-negative electrode lithium battery known by high energy density is again attracting much attention of researchers as the most potential battery system, and the battery can push the full battery energy density to be extremely good and is regarded as the ultimate choice of the high energy density lithium battery. However, compared to lithium batteries containing negative electrode materials, negative-electrode-less lithium batteries lose the protection of the negative electrode host material or lithium compensation from the negative electrode side, and any irreversible loss of active lithium during cycling is directly reflected in the loss of battery capacity, resulting in a lower capacity retention of the battery. Therefore, how to improve cycle life and inhibit growth of lithium dendrites while maintaining high energy density is the biggest challenge facing the current lithium metal batteries without negative electrodes.
Disclosure of Invention
The invention aims to solve the technical problem of providing a structure of a lithium battery without a negative electrode and a preparation method of the lithium battery without the negative electrode, and effectively overcomes the defects of the prior art.
The technical scheme for solving the technical problems is as follows:
the utility model provides a no negative pole lithium cell structure, includes the anodal mass flow body and the negative current collection body, the anodal mass flow body is equipped with negative pole lithium source coating outward, the negative current collection body is equipped with liquid metal coating outward, separate through the diaphragm with the mutual laminating of the two between the anodal mass flow body and the negative current collection body.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the liquid metal coating comprises the following materials in percentage by mass: ga 30-80%, In 5-40%, and Sn 1-20%.
Further, the negative current collector is a metal copper foil which is subjected to acid cleaning treatment and is coated with metal alloy on the surface.
Further, the acid used for the acid cleaning treatment is one or a combination of hydrochloric acid, hypochlorous acid, perchloric acid, hydrofluoric acid, sulfuric acid, carbonic acid, nitric acid, acetic acid and oxalic acid; the metal alloy material used for surface treatment of the metal copper foil is one or more of Ga, In and Sn, and is coated on the surface of the metal copper foil In one mode of spraying, dip-coating or electroplating.
Further, the positive current collector is a metal aluminum foil.
Further, the diaphragm is a ceramic diaphragm, the ceramic diaphragm comprises a support base material and a ceramic coating coated on the surface of the support base material, and the ceramic coating is a mixed coating of PVDF and ceramic.
The preparation method of the non-negative lithium battery is also provided, and the non-negative lithium battery is obtained by assembling the positive electrode material, the non-negative lithium battery structure and the electrolyte together.
Further, an electrolyte additive for stabilizing a negative electrode-electrolyte interface is added into the electrolyte, so that lithium is uniformly deposited on the surface of the metal copper foil.
Further, the electrolyte additive is one or more of lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (perfluoropinanyl) borate, lithium fluoroalkoxytrifluoroborate, lithium perchlorate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethanesulfonyl) imide.
Further, the anode material is one or a combination of lithium iron phosphate, lithium iron manganese phosphate, lithium cobalt oxide, lithium-rich manganese base, lithium nickel manganese cobalt oxide, lithium nickel aluminum cobalt oxide and lithium nickel manganese oxide
The beneficial effects are that: the problem that the energy density of the existing lithium battery is insufficient is solved, and the energy density is effectively improved.
Drawings
Fig. 1 is a schematic structural diagram of a structure of a lithium battery without a negative electrode according to the present invention.
In the drawings, the components represented by the respective reference numerals are listed below:
1. a positive current collector; 2. a negative current collector; 3. a liquid metal coating; 4. a cathode lithium source; 5. a diaphragm.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Examples
As shown in fig. 1, the non-negative lithium battery structure of this embodiment includes a positive current collector 1 and a negative current collector 2, a cathode lithium source 4 coating is provided outside the positive current collector 1, a liquid metal coating 3 is provided outside the negative current collector 2, and the positive current collector 1 and the negative current collector 2 are separated by a separator 5 attached to each other.
In the whole scheme, starting from the negative electrode side of the battery, firstly, the energy density of the battery is improved, and the negative electrode must be thinner, so that the traditional negative electrode graphite is abandoned, and a copper foil current collector which is electroplated with a layer of alloy is adopted for replacement, namely, the negative electrode current collector 2 is integrally designed into a liquid metal coating current collector (E-Cu) for inducing the epitaxial compact growth of lithium on the current collector, so that the generation of irreversible side reactions and dead lithium is reduced, the capacity retention rate of the lithium metal battery without the negative electrode is further improved, the energy density of the battery can be greatly increased, in addition, the mode can reduce a lot of material cost, reduce part of manufacturing processes, and shorten the manufacturing period.
More specifically, the liquid metal coating 3 comprises the following materials in percentage by mass: ga 30-80%, In 5-40% and Sn 1-20%, wherein the negative current collector 2 adopts a metal copper foil which is subjected to acid cleaning treatment and is coated with metal alloy on the surface, and the acid used In the acid cleaning treatment is one or a combination of hydrochloric acid, hypochlorous acid, perchloric acid, hydrofluoric acid, sulfuric acid, carbonic acid, nitric acid, acetic acid and oxalic acid; the metal alloy material used for the surface treatment of the metal copper foil is one or more of Ga, In and Sn (namely a liquid metal coating), and the metal alloy material is coated on the surface of the metal copper foil In one mode of spraying, dip-coating or electroplating, and more specifically:
the method comprises the following steps of ultrasonically soaking a metal copper foil with the thickness of 5-20 microns In an acid solution for 100-200 seconds to remove oil and a surface oxidation layer by acid washing, cleaning away residual acid solution by deionized water and absolute ethyl alcohol, drying at room temperature, coating an alloy material (a liquid metal coating 3) with the thickness of 0.5-10 microns on the surface, and compared with an original Cu current collector, starting storage of lithium by the liquid metal coating 3 through alloying reaction to form an epitaxial induction layer containing Ga, In and Sn on the surface of the negative current collector 2. The formed epitaxial inducing layer also has rapid lithium ion surface diffusion capacity, and lithium ions can flexibly migrate after reaching the current collecting surface, so that the lithium ions are effectively prevented from being reduced at a fixed site to form lithium dendrites.
In this embodiment, the positive current collector 1 is made of a metal aluminum foil.
In this embodiment, diaphragm 5 adopts ceramic diaphragm, specifically, ceramic diaphragm includes the supporting substrate and coats the ceramic coating on the supporting substrate surface, the ceramic coating is the mixed coating of PVDF and pottery, can let positive negative pole and diaphragm 3 laminate more tightly like this, reduces the formation of lithium dendrite, promotes battery rate performance simultaneously.
The preparation process of the lithium battery without the negative electrode comprises the following steps: assembling the positive electrode material, the structure of the non-negative lithium battery and the electrolyte together to obtain the non-negative lithium battery, wherein the assembling mode is approximately the same as the assembling mode of the existing lithium battery, and continuously overlapping the components according to the structure shown in the attached figure 1 in a winding or laminating mode to form the non-negative lithium battery.
In the preparation process of the battery, an electrolyte additive for stabilizing a negative electrode-electrolyte interface is added into the electrolyte, so that lithium is uniformly deposited on the surface of the metal copper foil. Starting from the electrolyte, adding an electrolyte additive for stabilizing a cathode-electrolyte interface, wherein the additive is decomposed, polymerized or adsorbed on the surface of the lithium cathode, and is used as a reactant to participate in the generation of an SEI film so as to change the composition and structure of the SEI film, modify the physical and chemical properties of the SEI film, and also can be used as a surfactant to change the reactivity of the surface of the lithium cathode, adjust the current distribution in the lithium deposition process and uniformly deposit the lithium. The electrolyte additive can improve the appearance of lithium deposition and the cycle efficiency even at the ppm level in the electrolyte. Therefore, modification of a lithium negative electrode using an electrolyte additive is the most economical and convenient method.
In this embodiment, the electrolyte additive is one or more of lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (perfluoropinanyl) borate, lithium fluoroalkoxytrifluoroborate, lithium perchlorate, lithium bis (fluorosulfonyl) imide, and lithium bis (trifluoromethanesulfonyl) imide.
In this embodiment, the positive electrode material is one or a combination of lithium iron phosphate, lithium iron manganese phosphate, lithium cobalt oxide, lithium manganese rich base, lithium nickel manganese cobalt oxide, lithium nickel aluminum cobalt oxide, and lithium nickel manganese oxide.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the present invention, unless otherwise expressly stated or limited, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through an intermediate. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A no negative pole lithium battery structure which characterized in that: including anodal mass flow body (1) and the negative pole mass flow body (2), anodal mass flow body (1) is equipped with negative pole lithium source (4) coating outward, the negative pole mass flow body (2) is equipped with liquid metal coating (3) outward, diaphragm (5) through laminating each other with the two between anodal mass flow body (1) and the negative pole mass flow body (2) separate.
2. The lithium battery structure without negative electrode as claimed in claim 1, characterized in that the liquid metal coating (3) comprises the following materials in mass percent: ga 30-80%, In 5-40%, and Sn 1-20%.
3. The lithium battery structure of claim 2, wherein: the negative current collector (2) is a metal copper foil which is subjected to acid cleaning treatment and is coated with metal alloy on the surface.
4. A non-negative electrode lithium battery cell structure as claimed in claim 3, wherein: the acid used for the acid cleaning treatment is one or a combination of hydrochloric acid, hypochlorous acid, perchloric acid, hydrofluoric acid, sulfuric acid, carbonic acid, nitric acid, acetic acid and oxalic acid; the metal alloy material used for surface treatment of the metal copper foil is one or more of Ga, In and Sn, and is coated on the surface of the metal copper foil In one mode of spraying, dip-coating or electroplating.
5. The lithium battery structure of claim 4, wherein: the positive current collector (1) is a metal aluminum foil.
6. The lithium battery structure of claim 5, wherein: the diaphragm (5) is a ceramic diaphragm, the ceramic diaphragm comprises a support base material and a ceramic coating coated on the surface of the support base material, and the ceramic coating is a mixed coating of PVDF and ceramic.
7. A preparation method of a lithium battery without a negative electrode is characterized in that: assembling together a positive electrode material, the negative-electrode free lithium battery structure of claim 6, and an electrolyte to obtain a negative-electrode free lithium battery.
8. The method of claim 7, wherein the method comprises: the electrolyte is added with an electrolyte additive for stabilizing a cathode-electrolyte interface so as to ensure that lithium is uniformly deposited on the surface of the metal copper foil.
9. The method of claim 8, wherein the method comprises: the electrolyte additive is one or more of lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (perfluoropinanyl) borate, lithium fluoroalkoxytrifluoroborate, lithium perchlorate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethanesulfonyl) imide.
10. The method of claim 7, wherein the method comprises: the anode material is one or a combination of lithium iron phosphate, lithium iron manganese phosphate, lithium cobalt oxide, a lithium-rich manganese base, lithium nickel manganese cobalt oxide, lithium nickel aluminum cobalt oxide and lithium nickel manganese oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111129015.4A CN114050308A (en) | 2021-09-26 | 2021-09-26 | Negative-electrode-free lithium battery structure and preparation method of negative-electrode-free lithium battery |
Applications Claiming Priority (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115101801A (en) * | 2022-06-29 | 2022-09-23 | 大连理工大学 | High-energy and high-safety lithium iron phosphate reference solid-state non-negative lithium battery and application thereof |
| CN115522205A (en) * | 2022-09-13 | 2022-12-27 | 云南中宣液态金属科技有限公司 | Liquid metal substrate cleaning method and integrated device for cleaning and coating |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130288122A1 (en) * | 2010-11-17 | 2013-10-31 | Mitsui Mining & Smelting Co., Ltd. | Copper foil for negative electrode current collector of lithium ion secondary battery, negative electrode material of lithium ion secondary battery, and method for selecting negative electrode current collector of lithium ion secondary battery |
| CN107615550A (en) * | 2016-05-06 | 2018-01-19 | 深圳先进技术研究院 | A kind of secondary cell and preparation method thereof |
| CN109728291A (en) * | 2018-12-29 | 2019-05-07 | 哈尔滨工业大学 | A kind of high specific energy lithium metal battery |
| CN113013417A (en) * | 2021-02-26 | 2021-06-22 | 山东大学 | Non-negative-electrode lithium metal battery, negative-electrode current collector and preparation method thereof |
| CN113036152A (en) * | 2021-03-08 | 2021-06-25 | 山东大学 | High-energy-density and high-safety zinc metal battery without negative electrode and preparation method and application thereof |
-
2021
- 2021-09-26 CN CN202111129015.4A patent/CN114050308A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130288122A1 (en) * | 2010-11-17 | 2013-10-31 | Mitsui Mining & Smelting Co., Ltd. | Copper foil for negative electrode current collector of lithium ion secondary battery, negative electrode material of lithium ion secondary battery, and method for selecting negative electrode current collector of lithium ion secondary battery |
| CN107615550A (en) * | 2016-05-06 | 2018-01-19 | 深圳先进技术研究院 | A kind of secondary cell and preparation method thereof |
| CN109728291A (en) * | 2018-12-29 | 2019-05-07 | 哈尔滨工业大学 | A kind of high specific energy lithium metal battery |
| CN113013417A (en) * | 2021-02-26 | 2021-06-22 | 山东大学 | Non-negative-electrode lithium metal battery, negative-electrode current collector and preparation method thereof |
| CN113036152A (en) * | 2021-03-08 | 2021-06-25 | 山东大学 | High-energy-density and high-safety zinc metal battery without negative electrode and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115101801A (en) * | 2022-06-29 | 2022-09-23 | 大连理工大学 | High-energy and high-safety lithium iron phosphate reference solid-state non-negative lithium battery and application thereof |
| CN115522205A (en) * | 2022-09-13 | 2022-12-27 | 云南中宣液态金属科技有限公司 | Liquid metal substrate cleaning method and integrated device for cleaning and coating |
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