CN114792848A - Storage battery capable of continuously supplementing lithium/sodium - Google Patents
Storage battery capable of continuously supplementing lithium/sodium Download PDFInfo
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- CN114792848A CN114792848A CN202110711214.XA CN202110711214A CN114792848A CN 114792848 A CN114792848 A CN 114792848A CN 202110711214 A CN202110711214 A CN 202110711214A CN 114792848 A CN114792848 A CN 114792848A
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- lithium
- pole piece
- sodium
- supplementing
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 159
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 71
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 71
- 239000011734 sodium Substances 0.000 title claims abstract description 71
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 49
- 238000003860 storage Methods 0.000 title claims abstract description 21
- 239000013589 supplement Substances 0.000 claims description 61
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 31
- 229910052782 aluminium Inorganic materials 0.000 claims description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 31
- 239000011889 copper foil Substances 0.000 claims description 22
- 239000011888 foil Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000004020 conductor Substances 0.000 claims description 14
- 239000007769 metal material Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 39
- 238000007599 discharging Methods 0.000 abstract description 6
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 45
- 239000007773 negative electrode material Substances 0.000 description 20
- 238000003475 lamination Methods 0.000 description 17
- 229940091252 sodium supplement Drugs 0.000 description 14
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 11
- 229910001415 sodium ion Inorganic materials 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 239000011149 active material Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000006138 lithiation reaction Methods 0.000 description 3
- 239000011868 silicon-carbon composite negative electrode material Substances 0.000 description 3
- 229910000681 Silicon-tin Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- LQJIDIOGYJAQMF-UHFFFAOYSA-N lambda2-silanylidenetin Chemical compound [Si].[Sn] LQJIDIOGYJAQMF-UHFFFAOYSA-N 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002733 tin-carbon composite material Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 238000003466 welding Methods 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- 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 & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Charge And Discharge Circuits For Batteries Or The Like (AREA)
Abstract
The invention provides a storage battery capable of continuously supplementing lithium/sodium, which relates to the technical field of storage batteries and has the following specific scheme: the utility model provides a can mend lithium battery in succession, includes positive plate I, negative pole piece I and at least one mends lithium pole piece, and arbitrary one mends lithium pole piece and all is connected with negative pole piece I through diode unit I, diode unit I includes at least one diode, mend lithium pole piece, diode unit I and negative pole piece I and pass through the wire and establish ties, diode unit I's positive pole switches on with negative pole piece I, and the negative pole switches on with mending lithium pole piece, mend lithium pole piece, positive plate I and negative pole piece I and keep apart through diaphragm I each other, mend lithium pole piece and set up the optional position in electric core inside. The lithium ion battery lithium supplementing system can realize real-time automatic lithium supplementing of the lithium ion battery, and greatly improves the reversible capacity, the charging and discharging coulombic efficiency, the cycling stability and the service life of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of storage batteries, in particular to a storage battery capable of continuously supplementing lithium/sodium.
Background
The lithium ion battery can cause irreversible consumption of positive active lithium due to the formation of a solid electrolyte interface film (SEI) on the surface of a negative active material in the first charge-discharge (formation) process, and the SEI film has the phenomena of repeated destruction and regeneration in the cycle process, thereby causing the reduction of the coulombic efficiency, reversible capacity, specific energy, cycle stability and cruising ability of the battery; sodium ion batteries also suffer from the same problems.
The pre-lithiation of the negative electrode is to add an additional lithium source to compensate the loss of active lithium ions in the positive electrode material when an SEI film is formed on the surface of the negative electrode, so that the reversible discharge capacity of the battery can be improved. The Chinese patent with application number of 201310094757.7 discloses a method for continuously supplementing lithium powder to two sides of a lithium ion battery negative plate, wherein the lithium powder is dispersed on the upper surface and the lower surface of the negative plate by combining an external electric field adsorption technology and a rolling technology. The Chinese patent with application number 201520748174.6 discloses a lithium-supplementing device for a lithium ion battery pole piece, which achieves the effect of supplementing lithium to an electrode piece by contacting a lithium supply device and the electrode piece in a lithium ion-containing electrolyte tank. The Chinese invention patent with the application number of 201910761270.7 discloses a lithium supplement device and a lithium supplement method for a lithium ion battery negative pole piece, and the lithium supplement process of the negative pole piece is completed by an electrochemical lithium supplement method. The chinese patent with application number 201210351225.2 discloses a method for supplementing lithium to a negative plate of a lithium ion battery, which sprays or drops an organic lithium solution on the surface of the negative plate in an inert atmosphere, so that lithium ions in the organic lithium solution are reduced into metal lithium and are inserted into the negative plate, thereby realizing the 'wet lithium supplementation'. The Chinese patent with the application number of 202010534027.4 discloses a composite lithium supplement agent and a preparation method and application thereof, wherein the composite lithium supplement agent consists of an inorganic salt compound, a catalyst and a conductive agent, the composite lithium supplement agent is added to one side of a positive pole piece or a diaphragm close to a positive pole, and in the process of charging a battery, the composite lithium supplement agent is decomposed to release active lithium ions to supplement lithium for the battery, so that the irreversible lithium loss of the negative pole of the battery during the first charge and discharge is compensated. The lithium supplement method can compensate the active lithium consumption in the first charge-discharge cycle process of the battery, improve the first coulombic efficiency and the discharge specific capacity of the battery, but cannot supplement lithium continuously in the cycle process of the lithium ion battery, still has the problem of continuous active lithium consumption in the cycle process of the battery, and cannot obtain ideal cycle performance. The Chinese patent with application number 201710116105.7 discloses a secondary battery with a lithium supplement electrode and a preparation method thereof, wherein a lithium supplement electrode sheet is introduced into the battery, and when the lithium supplement electrode sheet is connected with a positive electrode sheet or a negative electrode sheet through an electrode tab, the lithium supplement of the positive electrode or the lithium supplement of the negative electrode can be realized, the high coulombic efficiency is realized, and the cycle characteristic is improved; the lithium supplementing technology can supplement lithium for the battery for the first time or in a circulating process, but the lithium ion battery is integrated in an electronic device, the lithium supplementing process needs to be independently connected with a lithium supplementing electrode and a positive electrode or a negative electrode, the lithium supplementing process is very complicated, the operability in practical application is poor, and the real-time lithium supplementing of the battery cannot be realized. The reasonable in design's battery structure introduces and mends the lithium electrode, realizes the real-time automatic lithium of meneing of battery, can promote lithium ion battery's anodal active material utilization ratio and full battery specific energy, charge-discharge coulomb efficiency, cycle stability and life by a wide margin.
Disclosure of Invention
The first purpose of the invention is to solve the problem that the reversible capacity and the cycling stability of the lithium ion storage battery are reduced due to the consumption of active lithium for the first time and in the cycling process, and provide a storage battery structure capable of automatically supplementing lithium in real time.
The second purpose of the invention is to solve the problem that the reversible capacity and the circulation stability of the battery are reduced due to the consumption of active sodium in the first time and the circulation process of the sodium-ion storage battery, and provide a storage battery structure capable of automatically supplementing sodium in real time.
The utility model provides a can mend lithium battery in succession, includes positive plate I, negative pole piece I and at least one and mends lithium plate, and arbitrary one is mended lithium plate and all is connected with negative pole piece I through diode unit I, diode unit I includes at least one diode, mend lithium plate, diode unit I and negative pole piece I and pass through the wire and establish ties, diode unit I's positive pole switches on with negative pole piece I, and the negative pole switches on with mending lithium plate, mend lithium plate, positive plate I and negative pole piece I and keep apart through diaphragm I each other, mend lithium plate and set up the optional position in electric core inside.
Furthermore, the lithium supplementing pole piece is a metal lithium piece or a lithium-containing pole piece compounded with a conductive material.
Further, when the number of the diodes in the diode unit I is greater than 1, the diodes are connected in series or in parallel to ensure the normal operation of the lithium supplementing process.
Further, positive plate I includes lamination type positive plate, winding type positive plate or winding and lamination combined type positive plate, negative plate I includes lamination type negative plate, winding type negative plate or winding and lamination combined type negative plate.
Further, the active material in the negative plate I is one of a carbon-based negative electrode material, a silicon-based negative electrode material, a tin-based negative electrode material, a silicon-carbon composite negative electrode material, a tin-carbon composite negative electrode material and a silicon-tin composite negative electrode material.
Further, the conductive material comprises a conductive carbon material or a conductive metal material I, wherein the conductive metal material I comprises one of a copper foil, a foam copper, a copper mesh or a bag-type copper foil, the bag-type copper foil is a copper foil with a cavity, a lithium source is arranged in the cavity of the bag-type copper foil, and a through hole is formed in the surface of the bag-type copper foil and used for dissolving out lithium ions.
The utility model provides a can mend sodium battery in succession, includes positive plate II, negative pole piece II and at least one mends sodium pole piece, and arbitrary one mends sodium pole piece and all is connected with negative pole piece II through diode unit II, diode unit II includes at least one diode, mend sodium pole piece, diode unit II and negative pole piece II and pass through the wire and establish ties, diode unit II's positive pole and negative pole piece II switch on, and the negative pole switches on with mending sodium pole piece, mend sodium pole piece, positive plate II and negative pole piece II and keep apart through diaphragm II each other, mend sodium pole piece setting in the inside optional position of electricity core.
Furthermore, the sodium supplementing pole piece is a metal sodium piece or a sodium-containing pole piece compounded with a conductive material.
Further, when the number of the diodes in the diode unit II is greater than 1, the diodes are connected in series or in parallel to ensure the normal operation of the sodium supplementing process.
Further, positive plate II includes lamination formula positive plate, coiling formula positive plate or coiling and lamination combined type positive plate, negative plate II includes lamination formula negative pole piece, coiling formula negative pole piece or coiling and lamination combined type negative pole piece.
Further, the active material in the negative plate II is one or a combination of a carbon-based negative electrode material, a tin-based negative electrode material, and a transition metal phosphide negative electrode material.
Further, the conductive material comprises a conductive carbon material or a conductive metal material II, wherein the conductive metal material II comprises one of an aluminum foil, a foamed aluminum, an aluminum mesh or a bag-type aluminum foil, the bag-type aluminum foil is an aluminum foil with a chamber, a sodium source is arranged in the chamber of the bag-type aluminum foil, and through holes are formed in the surface of the bag-type aluminum foil and used for dissolving out sodium ions.
Compared with the prior art, the invention has the beneficial effects that:
the invention skillfully utilizes the positive characteristic in the volt-ampere characteristic of the diode, and connects the diode unit between the lithium supplement pole piece or the sodium supplement pole piece and the corresponding negative pole piece, wherein the anode of the diode unit is connected with the negative pole piece of the battery, and the cathode of the diode unit is connected with the corresponding lithium supplement pole piece or sodium supplement pole piece, thus realizing the real-time automatic sodium supplement of the lithium ion battery or the sodium ion battery. The invention can realize the real-time automatic lithium supplement or the real-time automatic sodium supplement of the lithium ion or sodium ion storage battery in any cycle process. The type, the number and the series-parallel connection mode of the diodes in the diode unit can be adjusted according to the working voltage characteristics of the lithium negative plate or the sodium negative plate to be supplemented, when the working voltage platform of the lithium negative electrode or the sodium negative electrode to be supplemented is high, the diode with high forward conduction voltage can be selected or a plurality of diodes with low forward conduction voltage can be connected in series, and when the working voltage platform of the lithium negative electrode or the sodium negative electrode to be supplemented is low, a single diode can be selected; when the current generated between the lithium supplement electrode or the sodium supplement electrode and the corresponding negative electrode in the lithium supplement or sodium supplement process is large, a high-power diode or a plurality of low-power diodes can be connected in parallel to reduce the running power of a single diode, so that the diodes are prevented from being burnt by large current. In addition, the lithium supplement pole piece or the sodium supplement pole piece and the diode unit can be packaged in the battery, and the lithium supplement or sodium supplement process does not need human intervention or special circuit arrangement and does not consume extra energy. Meanwhile, the thickness of the lithium supplement pole piece or the sodium supplement pole piece is gradually reduced in the circulation process, so that a certain free volume is released, and a certain buffer space is provided for the volume expansion of the battery, therefore, the problem of the volume expansion in the circulation process of the battery can be reduced. Compared with other one-time or stage lithium/sodium supplementing methods, the method can continuously compensate the loss of the active lithium/active sodium of the positive electrode in the circulating process, and greatly improves the utilization rate of the active substance of the positive electrode of the lithium/sodium ion storage battery, the specific energy of the battery, the charging and discharging coulombic efficiency, the circulating stability and the service life.
Drawings
FIG. 1: the invention relates to a structural schematic diagram of a storage battery capable of continuously supplementing lithium;
FIG. 2 is a schematic diagram: the invention relates to a structural schematic diagram of a storage battery capable of continuously supplementing sodium;
FIG. 3: a first charge-discharge curve diagram of a lithium cobaltate positive electrode-silicon monoxide negative electrode lithium ion battery; the solid line is the pole piece containing the lithium supplement, and the dotted line is the pole piece not containing the lithium supplement;
FIG. 4: a cycle performance diagram of the lithium cobaltate positive electrode-silicon monoxide negative electrode lithium ion battery containing the lithium supplement pole piece;
FIG. 5: a lithium cobaltate positive electrode-silicon monoxide negative electrode lithium ion battery cycle performance diagram without a lithium supplement pole piece;
in the figure: 1. a positive plate I; 2. a negative plate I; 3. supplementing a lithium pole piece; 4. a diode unit I; 5. a diaphragm I; 6. a positive plate II; 7. a negative plate II; 8. supplementing a sodium pole piece; 9. a diode unit II; 10. and a diaphragm II.
Detailed Description
Detailed description of the invention
The utility model provides a can mend lithium battery in succession, includes positive plate I1, negative pole piece I2, mends lithium pole piece 3 and diode unit I4, diode unit I4 includes at least one diode, mend lithium pole piece 3, diode unit I4 and negative pole piece I2 and pass through the wire and establish ties, diode unit I4's positive pole and negative pole piece I2 switch on, and the negative pole switches on with mending lithium pole piece 3, mend lithium pole piece 3, positive plate I1 and negative pole piece I2 and keep apart through diaphragm I5 each other.
Furthermore, the lithium supplement pole piece 3 is a metal lithium piece or a lithium-containing pole piece compounded with a conductive material, and the number, the position and the thickness of the lithium supplement pole pieces can be adjusted according to the capacity and the cycle life requirement of the battery so as to improve the lithium supplement efficiency. The conductive material comprises a conductive carbon material or a conductive metal material I, wherein the conductive metal material I comprises one of a copper foil, a foam copper, a copper mesh or a bag-type copper foil, the bag-type copper foil is a copper foil with a cavity, and a through hole is formed in the surface of the bag-type copper foil and is used for dissolving out lithium ions; the lithium-containing pole piece compounded with the conductive material can be a lithium-containing pole piece prepared by rolling or evaporating metal lithium on the surface of copper foil, a lithium-containing pole piece prepared by filling molten metal lithium in pores of foamed copper, a lithium-containing pole piece prepared by rolling and compounding metal lithium and a copper mesh or a lithium-containing pole piece obtained by placing a lithium source in a cavity of a bag-type copper foil. The lithium-supplement electrode sheet 3 is preferably a lithium-containing electrode sheet prepared after the surface of the copper foil is rolled or metal lithium is evaporated or a lithium source is placed in a cavity of the bag-type copper foil, and the lithium-containing electrode sheet and a copper current collector have high binding force, so that the structural stability of the lithium-supplement electrode and the utilization rate of the lithium source can be improved, and the continuous lithium supplement effect in the long-cycle process is ensured.
Further, when diode quantity in diode unit I4 is greater than 1, adopt series connection, parallelly connected or series connection and parallelly connected mode of combining between the diode to connect, when the operating voltage platform of waiting to mend the lithium negative pole is higher, the mode that the diode that adopts a plurality of low forward conduction voltages establishes ties can guarantee that it normally mends lithium, when the electric current that the lithium process produced of mending between lithium electrode and the negative pole is great, adopt parallelly connected mode can reduce the operating current of single diode, guarantee that the diode is not burnt by high power heating.
Further, positive plate I1 includes lamination formula positive plate, coiling formula positive plate or coiling and lamination combined type positive plate, negative plate I2 includes lamination formula negative pole piece, coiling formula negative pole piece or coiling and lamination combined type negative pole piece.
Further, the diode in the diode unit I4 may be a silicon diode or a germanium diode.
Preferably, the active material in the negative electrode piece I2 is one of a carbon-based negative electrode material, a silicon-based negative electrode material, a tin-based negative electrode material, a silicon-carbon composite negative electrode material, a tin-carbon composite negative electrode material, and a silicon-tin composite negative electrode material. The silicon-carbon composite negative electrode material or the silicon monoxide negative electrode material with 5-50% of silicon energy is preferably selected, the negative electrode material has high specific energy, the energy density of the battery can be obviously improved by matching with a high-voltage positive electrode, but the first cycle irreversible capacity of the negative electrode material is large, active lithium in the positive electrode can be continuously consumed due to the film forming problem of the surface of the negative electrode in the cycle process, and ideal cycle stability cannot be obtained.
Before the battery is charged and discharged for the first time, the electrode potential of the negative plate I2 is higher than the forward conduction voltage of the diode unit I4, the lithium supplement plate 3 is in electronic conduction with the negative plate I2, a battery structure of the lithium supplement plate 3-the diode unit I4-the negative plate I2 is formed in the battery, the lithium supplement plate 3 is dissolved to supplement lithium for the negative plate I2 and is used for forming a negative SEI film, and when the electrode potential of the negative plate I2 is reduced to enter a dead zone voltage interval of the diode unit I4, an electronic channel between the lithium supplement plate 3 and the negative plate I2 is automatically closed; in the charging process of the battery, the active material in the negative plate I2 is subjected to lithiation reaction, the electrode potential of the negative plate I2 is further reduced, and the diode unit I4 is always in a closed state, so that the lithium supplement electrode plate 3 does not participate in the charging process of the battery; in the process of battery discharge, lithium ions are dissolved out from the negative electrode, the electrode potential of the negative plate I2 is gradually increased, when the electrode potential of the negative plate I2 exceeds the upper limit voltage of the dead zone voltage interval of the diode unit I4, the lithium supplement plate 3 is in electronic conduction with the corresponding negative plate I2, the lithium supplement plate 3 is dissolved and releases lithium ions, the loss of active lithium ions of the positive electrode in the charging process is compensated, and the negative plate I2 and the diode unit I4 are kept in electronic conduction until the battery discharge process is finished.
Detailed description of the invention
The utility model provides a can mend battery of sodium in succession, includes positive plate II 6, negative pole piece II 7, mends sodium pole piece 8 and diode unit II 9, diode unit II 9 includes at least one diode, mend sodium pole piece 8, diode unit II 9 and pass through the wire with negative pole piece II 7 and establish ties, diode unit II 9's positive pole and negative pole piece II 7 switch on, and the negative pole switches on with mending sodium pole piece 8, mend sodium pole piece 8, positive plate II 6 and negative pole piece II 7 and keep apart through diaphragm II 10 each other.
Furthermore, mend sodium pole piece 8 and be metal sodium piece or contain the sodium pole piece with conducting material complex, mend the quantity, position and the thickness of sodium pole piece and can adjust according to the capacity and the cycle life requirement of battery to promote and mend sodium efficiency. The conductive material comprises a conductive carbon material or a conductive metal material II, wherein the conductive metal material II comprises one of an aluminum foil, foamed aluminum, an aluminum mesh or a bag-type aluminum foil, the bag-type aluminum foil is an aluminum foil with a cavity, and through holes are formed in the surface of the bag-type aluminum foil and used for dissolving out sodium ions; the sodium-containing pole piece compounded with the conductive material can be a sodium-containing pole piece prepared by rolling or evaporating metal sodium on the surface of an aluminum foil, a sodium-containing pole piece prepared by filling molten metal sodium into pores of foamed aluminum, a sodium-containing pole piece prepared by rolling and compounding metal sodium and an aluminum mesh or a sodium-containing pole piece obtained by placing a sodium source in a cavity of a bag-type aluminum foil. The sodium-supplementing pole piece 8 is preferably a sodium-containing pole piece prepared by rolling or evaporating the metal sodium on the surface of the aluminum foil or a sodium-containing pole piece obtained by placing a sodium source in a bag-type aluminum foil chamber, and the sodium-containing pole piece and an aluminum current collector have high binding force, so that the structural stability of the sodium-supplementing electrode and the utilization rate of the sodium source can be improved, and the continuous sodium-supplementing effect in the long-circulating process is ensured.
Furthermore, when the number of the diodes in the diode unit II 9 is larger than 1, the diodes are connected in series, in parallel or in combination of series connection and parallel connection, when the working voltage platform of the negative electrode of the sodium to be supplemented is higher, the diodes with low forward conduction voltage are connected in series, and when the current generated in the sodium supplementing process between the sodium supplementing electrode and the negative electrode is larger, the working current of a single diode can be reduced by adopting the parallel connection mode, so that the diodes are prevented from being burnt by high-power heating.
Further, positive plate II 6 includes lamination formula positive plate, coiling formula positive plate or coiling and lamination combined type positive plate, negative plate II 7 includes lamination formula negative pole piece, coiling formula negative pole piece or coiling and lamination combined type negative pole piece.
Further, the diode in the diode unit II 9 may be a silicon diode or a germanium diode.
Preferably, the active material in the negative electrode sheet II 7 is one or a combination of carbon-based negative electrode material, tin-based negative electrode material, and transition metal phosphide negative electrode material.
Before the battery is charged and discharged for the first time, the electrode potential of the negative plate II 7 is higher than the forward conduction voltage of the diode unit II 9, the sodium supplement plate 8 is in electronic conduction with the negative plate II 7, a battery structure of the sodium supplement plate 8-the diode unit II 9-the negative plate II 7 is formed in the battery, the sodium supplement plate 8 is dissolved to supplement sodium for the negative plate II 7 and is used for forming a negative SEI film, and when the electrode potential of the negative plate II 7 is reduced and enters a dead zone voltage interval of the diode unit II 9, an electronic channel between the sodium supplement plate 8 and the negative plate II 7 is automatically closed; in the charging process of the battery, the active material in the negative plate II 7 is subjected to sodium modification reaction, the electrode potential of the negative plate II 7 is further reduced, and the diode unit II 9 is always in a closed state, so that the sodium supplement plate 8 does not participate in the charging process of the battery; in the process of battery discharge, sodium ions are dissolved out from the negative electrode, the electrode potential of the negative plate II 7 is gradually increased, when the electrode potential of the negative plate II 7 exceeds the upper limit voltage of the dead zone voltage interval of the diode unit II 9, the sodium supplementing plate 8 is in electronic conduction with the corresponding negative plate II 7, the sodium supplementing plate 8 is dissolved and releases sodium ions, the loss of positive active sodium ions in the charging process is compensated, and the negative plate II 7 and the diode unit II 9 are kept in electronic conduction until the battery discharge process is finished.
Example 1
The surface capacity is 4.1mAh/cm 2 The size of the lithium cobaltate anode is 6.3cm multiplied by 4.5cm, the capacity of the single-side coated lithium cobaltate anode is 4.305mAh/cm 2 The method comprises the following steps of coating a single-side coated silicon monoxide negative electrode lamination with the size of 6.5cm multiplied by 4.7cm, placing a lithium-containing pole piece with 20 mu m lithium metal rolled on the surface of copper foil as a lithium supplement pole piece 3 on the non-coating side of the silicon monoxide negative pole piece, isolating electrodes by adopting a commercial diaphragm, connecting a silicon diode (with the forward conduction voltage of 0.7V and the rated power of 0.5W) in series between the negative pole piece 2 and the lithium supplement pole piece 3 by adopting a lead, placing a laminated cell in an aluminum plastic film shell, respectively welding a lug on the positive pole piece 1 and the negative pole piece 2, packaging after vacuum liquid injection, standing for 90 hours at room temperature, and then carrying out a charge-discharge cycle test, wherein the charge-discharge multiplying power is 0.2C, the charge-discharge interval is 2.5-4.48V, and the test temperature is room temperature.
Comparative example 1
The structure of the lithium ion battery is the same as that of the lithium ion battery in the embodiment 1, except that the lithium supplement plate 3 and the diode unit I4 are not contained in the battery cell of the lithium ion battery in the comparative example, the battery is subjected to charge and discharge cycle test after being placed at room temperature for 90 hours after being injected and packaged, the charge and discharge multiplying power is 0.2C, the charge and discharge interval is 2.5-4.48V, and the test temperature is room temperature.
As can be seen from fig. 3, the initial charging voltage value of the lithium ion battery without the lithium supplement pole piece 3 is about 0.3V, and after the lithium ion battery with the lithium supplement pole piece 3 is left to stand for 90 hours, the initial charging voltage of the battery is about 2.5V, and the slow voltage rise time in the early stage of charging is greatly shortened, which all proves that the lithium supplement pole piece 3 performs effective pre-lithiation on the silicon oxide negative pole piece in the early stage standing process; in addition, the lithium ion battery containing the lithium supplement electrode plate 3 has smaller electrochemical polarization in the charging and discharging processes, the first charging and discharging capacity is 110.883mAh and 83.088mAh respectively, the coulombic efficiency is 74.933%, while the lithium ion battery without the lithium supplement electrode plate 3 has the first charging and discharging capacity of only 104.7mAh and 72.15mAh, and the first charging and discharging coulombic efficiency is only 68.934%.
Fig. 4 and fig. 5 are a cycle performance diagram of a lithium cobalt oxide positive electrode-silicon monoxide negative electrode lithium ion battery including the lithium supplement electrode piece 3 and a cycle performance diagram of a lithium cobalt oxide positive electrode-silicon monoxide negative electrode lithium ion battery not including the lithium supplement electrode piece 3, respectively, and it can be known from the diagrams that the cycle stability of the lithium ion battery including the lithium supplement electrode piece 3 is obviously superior to that of the lithium ion battery not including the lithium supplement electrode piece 3, and the average coulombic efficiency of the lithium ion battery including the lithium supplement electrode piece 3 in the previous 24 cycles is 98.24%, which is obviously superior to that of the lithium ion battery not including the lithium supplement electrode piece 3, which proves that the lithium supplement electrode piece 3 can continuously supplement lithium to the battery in the cycles, thereby improving the cycle stability of the battery.
Claims (10)
1. The storage battery capable of continuously supplementing lithium comprises a positive plate I (1) and a negative plate I (2), and is characterized in that: the storage battery capable of continuously supplementing lithium further comprises at least one lithium supplementing pole piece (3), any one lithium supplementing pole piece (3) is connected with the negative pole piece I (2) through a diode unit I (4), the diode unit I (4) comprises at least one diode, the lithium supplementing pole piece (3), the diode unit I (4) and the negative pole piece I (2) are connected in series through a lead, the anode of the diode unit I (4) is conducted with the negative pole piece I (2), and the cathode of the diode unit I (4) is conducted with the lithium supplementing pole piece (3).
2. The storage battery capable of continuously supplementing lithium according to claim 1, characterized in that: the lithium supplement pole piece (3) is a metal lithium piece or a lithium-containing pole piece compounded with a conductive material.
3. The storage battery capable of continuously supplementing lithium according to claim 1, characterized in that: when the number of the diodes in the diode unit I (4) is more than 1, the diodes are connected in series or in parallel.
4. The storage battery capable of continuously supplementing lithium according to claim 1, characterized in that: the positive plate I (1) comprises a laminated positive plate, a wound positive plate or a wound and laminated combined positive plate, and the negative plate I (2) comprises a laminated negative plate, a wound negative plate or a wound and laminated combined negative plate.
5. The storage battery capable of continuously supplementing lithium according to claim 2, characterized in that: the conductive material comprises a conductive carbon material or a conductive metal material I, wherein the conductive metal material I comprises one of a copper foil, a foam copper, a copper mesh or a bag-type copper foil, the bag-type copper foil is a copper foil with a cavity, a lithium source is arranged in the cavity of the bag-type copper foil, and a through hole is formed in the surface of the bag-type copper foil.
6. The utility model provides a can mend battery of sodium in succession, includes positive plate II (6), negative pole piece II (7), its characterized in that: the storage battery capable of continuously supplementing sodium further comprises at least one sodium supplementing pole piece (8), any one sodium supplementing pole piece (8) is connected with the negative pole piece II (7) through a diode unit II (9), the diode unit II (9) comprises at least one diode, the sodium supplementing pole piece (8), the diode unit II (9) and the negative pole piece II (7) are connected in series through a lead, the anode of the diode unit II (9) is conducted with the negative pole piece II (7), and the cathode is conducted with the sodium supplementing pole piece (8).
7. The accumulator capable of continuously supplementing sodium according to claim 6, characterized in that: the sodium supplementing pole piece (8) is a metal sodium piece or a sodium-containing pole piece compounded with a conductive material.
8. The accumulator capable of continuously supplementing sodium according to claim 6, characterized in that: and when the number of the diodes in the diode unit II (9) is more than 1, the diodes are connected in series or in parallel.
9. The accumulator capable of continuously supplementing sodium according to claim 6, characterized in that: the positive plate II (6) comprises a laminated positive plate, a wound positive plate or a wound and laminated combined positive plate, and the negative plate II (7) comprises a laminated negative plate, a wound negative plate or a wound and laminated combined negative plate.
10. The accumulator capable of continuously supplementing sodium according to claim 7, characterized in that: the conductive material comprises a conductive carbon material or a conductive metal material II, wherein the conductive metal material II comprises one of an aluminum foil, a foamed aluminum, an aluminum mesh or a bag-type aluminum foil, the bag-type aluminum foil is an aluminum foil with a chamber, a sodium source is arranged in the chamber of the bag-type aluminum foil, and through holes are formed in the surface of the bag-type aluminum foil.
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| PCT/CN2021/135401 WO2022156383A1 (en) | 2021-01-25 | 2021-12-03 | Storage battery capable of being continuously supplemented lithium/sodium |
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| CN115332725A (en) * | 2022-08-22 | 2022-11-11 | 珠海冠宇动力电池有限公司 | Diaphragm and battery |
| CN115473008B (en) * | 2022-09-28 | 2023-08-01 | 东莞正力新能电池技术有限公司 | Lithium supplementing type isolating film, battery core and secondary battery |
| CN115395116B (en) * | 2022-10-26 | 2023-01-20 | 星恒电源股份有限公司 | Positive pole piece of sodium-ion battery, preparation method of positive pole piece and sodium-ion battery |
| CN116789191B (en) * | 2023-07-25 | 2024-01-12 | 宁德时代新能源科技股份有限公司 | Sodium supplementing material, preparation method thereof, positive electrode plate, electrode assembly, battery and electricity utilization device |
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