CN106684298B - Application method of lithium ion battery - Google Patents
Application method of lithium ion battery Download PDFInfo
- Publication number
- CN106684298B CN106684298B CN201710053775.9A CN201710053775A CN106684298B CN 106684298 B CN106684298 B CN 106684298B CN 201710053775 A CN201710053775 A CN 201710053775A CN 106684298 B CN106684298 B CN 106684298B
- Authority
- CN
- China
- Prior art keywords
- negative electrode
- insulating layer
- layer
- lithium ion
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 87
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims description 31
- 229910052744 lithium Inorganic materials 0.000 claims description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- -1 polyethylene terephthalate Polymers 0.000 claims description 20
- 238000002161 passivation Methods 0.000 claims description 15
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 230000002441 reversible effect Effects 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 14
- 238000012544 monitoring process Methods 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 186
- 239000011248 coating agent Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 20
- 210000001787 dendrite Anatomy 0.000 description 18
- 239000004743 Polypropylene Substances 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 229920000049 Carbon (fiber) Polymers 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Images
Classifications
-
- 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
- H01M50/411—Organic material
-
- 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
- H01M50/44—Fibrous material
-
- 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
-
- 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
-
- 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
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery diaphragm and application thereof. Compared with the prior art, on one hand, the carbon material used in the porous conducting layer has high flexibility, and the flexibility and the stability of the diaphragm can be improved; the carbon material has rich micropores, which is beneficial to the transmission of lithium ions, and meanwhile, the conductive carbon material is used in both the positive electrode and the negative electrode, so that the conductive carbon material has better compatibility with the internal system of the battery, and can exist stably without affecting the safety performance of the battery; on the other hand, the porous conducting layer has the function of monitoring the internal parameters of the battery, which is not possessed by the traditional diaphragm, and the function can avoid the safety problem caused by the internal short circuit of the lithium ion battery as much as possible.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an application method of a lithium ion battery.
Background
Lithium ion batteries are widely used due to their characteristics of high voltage, high specific energy, long life, no memory effect, small self-discharge, etc., however, portable electronic devices have increasingly high requirements for energy density and charging speed of lithium ion batteries.
Among them, the negative electrode material has a great influence on the energy density of the lithium ion battery. The negative electrode materials of the lithium ion battery which are commercialized at present are generally graphite, silicon alloy, tin alloy and the like, but the theoretical energy density of the negative electrode materials is lower than that of metal lithium. Therefore, in recent years, research and commercialization of lithium ion batteries using metallic lithium as a negative electrode material are actively underway. At present, in the application of lithium ion batteries, the main problem that metal lithium cannot be popularized as a negative electrode material is safety.
It is well known that when a lithium ion battery is charged, a positive electrode active material loses electrons to generate lithium ions, and at the same time, Li+The electrolyte penetrates through a solid electrolyte membrane (SEI film) on the surface of the negative active material to reach the inside of the negative active material and is subjected to reduction reaction with the negative active material, so that electrons are obtained, and lithium metal or lithiated graphite and the like are generated. In fact, for a lithium metal negative electrode, the charging process is a process of reducing and depositing lithium ions on the negative electrode side, and the negative electrode side can cause the growth of lithium dendrites during repeated charging and discharging due to uneven current density distribution on a microscopic scale. When the lithium dendrite completely penetrates through the diaphragm and contacts with the anode, micro short circuit is caused if the lithium dendrite is light, so that the self-discharge of the battery is enlarged; if so, thermal runaway of the battery is caused, and the battery is ignited and exploded.
Although there are many related studies and reports for inhibiting the growth of lithium dendrites in lithium ion batteries, none of them has been taken out of the laboratory, and no commercial products are yet available. For example, the Chinese patent with the patent application number of 201410165195.5 adds an inorganic coating on the diaphragm; also, chinese patent application No. 201310147483.3 utilizes ceramic to increase the strength of the diaphragm; the diaphragm has a certain effect of slowing down the growth of lithium dendrites, but the actual effect is not obvious. In addition, chinese patent publication No. CN 105226226A provides a method for monitoring short circuit of a battery by disposing a metal layer between two separator substrates. The diaphragm can monitor the occurrence of short circuit in the battery to a certain extent; however, the metal layer provided in the middle of the separator has the following problems:
1) the diaphragm must have micropores to ensure that lithium ions can freely move back and forth between the positive electrode and the negative electrode; the metal is compact, namely a barrier layer is added in the middle of the diaphragm, so that the shuttling difficulty of lithium ions is greatly increased;
2) the metal has poor flexibility, and the good flexibility characteristic of the diaphragm is difficult to meet; the difficulty of compounding the metal on the insulating substrate is high, the bonding strength is low, and the interlayer peeling problem is easy to occur;
3) the thickness of the metal layer cannot be made very thin unless electroplating is adopted, but the electroplating operation on the insulated diaphragm substrate is difficult;
4) since the metal itself has an electrochemical window, the provision of a metal layer in the separator, which is equivalent to the introduction of an impurity source into the battery, is dangerous and has low reliability and safety.
In view of the above, there is a need for further improvement of the existing separator, thereby improving the safety performance of the lithium ion battery, especially the lithium ion battery using metallic lithium as the negative electrode.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the lithium ion battery diaphragm is provided to improve the safety performance of the lithium ion battery using the diaphragm.
The utility model provides a lithium ion battery diaphragm, includes positive insulating layer, negative pole insulating layer and sets up positive insulating layer with porous conducting layer between the negative pole insulating layer, porous conducting layer is at least one kind in graphite alkene layer, carbon fiber layer, carbon nanotube layer and the conductive carbon layer.
Compared with metal, the carbon material such as graphene, carbon fiber, carbon nanotube and conductive carbon has abundant micropores, and can completely meet the requirement of lithium ion transmission; secondly, the carbon material has better flexibility, meets the requirement of the diaphragm on the flexibility, enables the diaphragm to be more easily compounded with an insulating matrix to form a sandwich-shaped diaphragm structure, and is not easy to generate the interlayer stripping phenomenon; and the carbon material layer can be made very thin, the difficulty coefficient of the specific operation is lower than that of the coating metal, and the conductive carbon material is used in the positive electrode and the negative electrode, so that the conductive carbon material has better compatibility with the internal material of the battery, can stably exist, and cannot cause side reaction to influence the safety performance of the battery.
The porous conducting layer can be coated on the surface of the positive/negative electrode insulating layer in a dipping coating, spraying coating, casting coating or transfer coating mode, and then the negative/positive electrode insulating layer is hot-pressed on the porous conducting layer; thus obtaining the sandwich-shaped diaphragm structure of the anode insulating layer, the porous conducting layer and the cathode insulating layer. The positive insulating layer and the negative insulating layer can isolate electrons and transmit lithium ions; the porous conductive layer can then monitor the internal parameters of the cell. Because the porous conducting layer and the negative electrode have chemical potential change in the process that the lithium dendrite is generated to pierce through the negative electrode insulating layer of the diaphragm to the porous conducting layer, the condition of short circuit is monitored by utilizing the obvious change of the potential, and the more serious result caused by the short circuit is avoided.
As an improvement of the lithium ion battery diaphragm, the anode insulating layer and the cathode insulating layer are at least one of a porous polyolefin film, a polyethylene terephthalate film, a polyvinylidene fluoride film, a polyamide film, a polyimide film and a ceramic film layer. The positive and negative insulating layers have the functions of isolating electrons and transmitting ions.
As an improvement of the lithium ion battery diaphragm, the thickness of the porous conducting layer is 0.001-5 mu m. If the porous conductive layer is too thin; the mechanical property of the diaphragm is reduced, and the diaphragm can not be used as a conductive layer to monitor the internal parameters of the battery; if the porous conductive layer is too thick, the energy density of the battery may be affected.
As an improvement of the lithium ion battery diaphragm, the thickness of the porous conducting layer is 0.1-3 mu m, and preferably 1-3 mu m.
As an improvement of the lithium ion battery diaphragm, the thicknesses of the positive electrode insulating layer and the negative electrode insulating layer are both 1-25 mu m. The thicknesses of the anode insulating layer and the cathode insulating layer can be selected according to the type of the lithium ion battery, and the thicknesses are not suitable to be too thick in order to improve the energy density of the lithium ion battery.
As an improvement of the lithium ion battery separator, the porosity of the porous conducting layer is 10-85%, and preferably 30-60%. If the porosity of the porous conducting layer is too low, the transmission of lithium ions is influenced; if the porosity is too high, the stability of the separator structure is impaired, and the conductive ability of the conductive layer is lowered.
The second purpose of the invention is: the lithium ion battery comprises a positive electrode, a negative electrode, an isolating membrane arranged between the positive electrode and the negative electrode, and electrolyte, wherein the isolating membrane is the lithium ion battery diaphragm in any section, and a porous conducting layer of the isolating membrane is electrically connected with a conducting lead to form a diaphragm electrode. The conductive leads may be made of metal, alloy, or other materials with good conductivity.
The invention introduces a diaphragm electrode besides the anode and the cathode of the traditional battery by a method of arranging the porous conducting layer in the diaphragm structure. So that one or comprehensive detection of voltage, resistance, current, capacitance and other parameters can be established between the diaphragm electrode and the negative electrode; when the battery is charged, the parameters are detected, and an alarm is given after the fact that the lithium dendrite grows to be in contact with the porous conducting layer of the diaphragm, so that a user is prompted to take measures of stopping continuous use and the like, and the problem of safety caused by the fact that the lithium dendrite further grows to the positive electrode is prevented. In addition, a positive voltage (namely, the separator is connected with a high potential, and the negative electrode is connected with a low potential) can be applied between the separator and the negative electrode to prevent the negative electrode lithium metal from discharging to the porous conducting layer of the separator, so that the growth of lithium dendrites to the direction of the separator is inhibited, and the safety performance and the service life of the lithium ion battery are improved.
Preferably, the negative electrode material used for the negative electrode is metallic lithium. Compared with negative electrode materials such as graphite, silicon alloy, tin alloy and the like, the lithium metal has higher theoretical energy density, so that the energy density and the rate capability of the lithium ion battery can be greatly improved.
The third purpose of the invention is that: the method for monitoring the short circuit of the battery by applying the lithium ion battery comprises the following steps:
firstly, measuring the potential difference between a diaphragm electrode and a negative electrode by a voltage monitor, and recording the measured value as Vm；
And step two, when Vm approaches zero, the fact that the lithium dendrite pierces through the negative electrode insulating layer of the diaphragm and contacts the porous conducting layer is judged, and the battery is about to be short-circuited.
Because the porous conducting layer and the negative electrode have chemical potential change in the process that the lithium dendrite is generated to pierce through the negative electrode insulating layer of the diaphragm to the porous conducting layer, the condition of short circuit is monitored by utilizing the obvious change of the potential, so that the battery cell can be timely detached or safely processed before the short circuit occurs, and the occurrence of safety accidents is effectively avoided.
The fourth purpose of the invention is that: the method for passivating the negative electrode by applying the lithium ion battery comprises the following steps:
step one, setting the charging voltage between the positive electrode and the negative electrode as V1Charging current is I1In which V is1＞0，I1＞0；
Step two, applying a positive passivation voltage V between the diaphragm electrode and the negative electrode during battery charging2And forward passivation current I2In which V is2＞V1，I2＜I1(ii) a Applying a forward passivation voltage V between the separator and negative electrodes during non-battery charging3And forward passivation current I3In which V is3＞0，I3＞0。
By continuously introducing forward passivation current between the diaphragm electrode and the negative electrode, lithium ions can be uniformly deposited on the negative electrode under low current density, and the generation of lithium dendrites is avoided.
Preferably, step two is as described in I2Less than or equal to 0.05C, said I3Less than or equal to 0.05C; among them, the passivation effect is more sufficient when the current is smaller.
The fifth purpose of the inventionThe method comprises the following steps: the method for supplementing lithium to the battery by applying the lithium ion battery comprises the following steps: first, a reverse voltage V is applied between the positive electrode and the negative electrode4In which V is4Less than 0; while applying a forward voltage V between the separator and the negative electrode5In which V is5Is greater than 0. Applying a reverse voltage V between the positive and negative electrodes4The purpose of this is that the negative electrode metal lithium can replenish the positive electrode or the electrolyte with lithium ions; and a positive voltage V is applied between the diaphragm and the negative electrode5The purpose of (1) is to avoid deposition of lithium ions on the separator.
The invention has the beneficial effects that: the invention relates to a lithium ion battery diaphragm which comprises a positive insulating layer, a negative insulating layer and a porous conducting layer arranged between the positive insulating layer and the negative insulating layer, wherein the porous conducting layer is at least one of a graphene layer, a carbon fiber layer, a carbon nanotube layer and a conducting carbon layer. According to the invention, the porous conducting layer is arranged between the two insulating layers of the diaphragm, on one hand, compared with a metal material, the carbon material used for the porous conducting layer has high flexibility, and the flexibility and the stability of the diaphragm can be improved; the carbon material has rich micropores, so that the transmission of lithium ions is not hindered, and meanwhile, the conductive carbon material is used in both the positive electrode and the negative electrode, so that the conductive carbon material has better compatibility with an internal system of the battery, can exist stably and does not influence the safety performance of the battery; on the other hand, the porous conducting layer has the function of monitoring the internal parameters of the battery, which is not possessed by the traditional diaphragm, and the function can avoid the safety accident problem caused by the short circuit of the lithium ion battery as much as possible.
Drawings
Fig. 1 is a schematic structural diagram of a lithium ion battery separator according to the present invention.
Fig. 2 is a schematic structural diagram of a lithium ion battery according to the present invention.
Fig. 3 is a schematic structural diagram of the lithium ion battery in the application process of the invention.
In the figure: 1-a positive electrode insulating layer; 2-a negative electrode insulating layer; 3-a porous conductive layer; 4-a lithium ion battery; 5-positive electrode; 6-negative pole; 7-diaphragm pole.
Detailed Description
The present invention and its advantageous effects will be described in detail below with reference to the accompanying drawings and embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
As shown in fig. 1, a lithium ion battery separator includes a positive insulating layer 1, a negative insulating layer 2, and a porous conductive layer 3 disposed between the positive insulating layer 1 and the negative insulating layer 2, wherein the porous conductive layer 3 is a graphene layer, and the positive insulating layer 1 and the negative insulating layer 2 are both polypropylene films; the specific preparation method is that the graphene layer can be coated on the surface of a polypropylene film in a dipping coating, spray coating, flow casting coating or transfer coating mode, and then another polypropylene film is hot-pressed on the graphene layer; thus obtaining the sandwich-shaped diaphragm of the anode insulating layer 1, the porous conducting layer 3 and the cathode insulating layer 2. Wherein, the thickness of the anode insulating layer 1 and the cathode insulating layer 2 of the obtained diaphragm is 8 μm; the thickness of the porous conductive layer 3 was 0.5 μm, and the porosity of the porous conductive layer 3 was 30%.
Example 2
A lithium ion battery diaphragm comprises a positive electrode insulating layer 1, a negative electrode insulating layer 2 and a porous conducting layer 3 arranged between the positive electrode insulating layer 1 and the negative electrode insulating layer 2, wherein the porous conducting layer 3 is a carbon fiber layer, the positive electrode insulating layer 1 is a polypropylene film, and the negative electrode insulating layer 2 is a polyethylene terephthalate film; the specific manufacturing method is that the carbon fiber layer can be coated on the surface of the polypropylene film in a dipping coating, spraying coating, tape casting coating or transfer coating mode, and then the polyethylene terephthalate film is hot-pressed on the carbon fiber layer; thus obtaining the sandwich-shaped diaphragm of the anode insulating layer 1, the porous conducting layer 3 and the cathode insulating layer 2. Wherein, the thickness of the anode insulating layer 1 and the cathode insulating layer 2 of the obtained diaphragm is 15 μm; the thickness of the porous conductive layer 3 was 2 μm, and the porosity of the porous conductive layer 3 was 50%.
Example 3
A lithium ion battery diaphragm comprises a positive electrode insulating layer 1, a negative electrode insulating layer 2 and a porous conducting layer 3 arranged between the positive electrode insulating layer 1 and the negative electrode insulating layer 2, wherein the porous conducting layer 3 is a carbon nanotube layer, the positive electrode insulating layer 1 is a polyimide film, and the negative electrode insulating layer 2 is a polyethylene film; the specific manufacturing method is that the carbon nano tube layer can be coated on the surface of the polyimide film in a dipping coating, spraying coating, curtain coating or transfer coating mode, and then the polyethylene film is hot-pressed on the carbon nano tube layer; thus obtaining the sandwich-shaped diaphragm of the anode insulating layer 1, the porous conducting layer 3 and the cathode insulating layer 2. Wherein, the thickness of the anode insulating layer 1 of the obtained diaphragm is 8 μm, and the thickness of the cathode insulating layer 2 is 10; the thickness of the porous conductive layer 3 was 3 μm, and the porosity of the porous conductive layer 3 was 40%.
Example 4
A lithium ion battery diaphragm comprises a positive electrode insulating layer 1, a negative electrode insulating layer 2 and a porous conducting layer 3 arranged between the positive electrode insulating layer 1 and the negative electrode insulating layer 2, wherein the porous conducting layer 3 is a conducting carbon layer, the positive electrode insulating layer 1 is a polyamide film, and the negative electrode insulating layer 2 is a polyvinylidene fluoride film; the preparation method comprises the following steps that the conductive carbon layer can be coated on the surface of the polyamide film in a dipping coating, spraying coating, casting coating or transfer coating mode, and then the polyvinylidene fluoride film is hot-pressed on the conductive carbon layer; thus obtaining the sandwich-shaped diaphragm of the anode insulating layer 1, the porous conducting layer 3 and the cathode insulating layer 2. Wherein, the thickness of the anode insulating layer 1 of the obtained diaphragm is 10 μm, and the thickness of the cathode insulating layer 2 is 15; the thickness of the porous conductive layer 3 was 4 μm, and the porosity of the porous conductive layer 3 was 60%.
Example 5
Unlike example 1, the positive electrode insulating layer 1 and the negative electrode insulating layer 2 of the obtained separator each had a thickness of 25 μm; the thickness of the porous conductive layer 3 was 5 μm, and the porosity of the porous conductive layer 3 was 85%.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
Unlike example 2, the thickness of each of the positive electrode insulating layer 1 and the negative electrode insulating layer 2 of the obtained separator was 1 μm; the thickness of the porous conductive layer 3 was 0.001 μm, and the porosity of the porous conductive layer 3 was 10%.
The rest is the same as embodiment 2, and the description is omitted here.
Example 7
Unlike example 3, the negative electrode insulating layer 2 was a ceramic film layer, and the thickness of the positive electrode insulating layer 1 of the obtained separator was 6 μm and the thickness of the negative electrode insulating layer 2 was 12 μm; the thickness of the porous conductive layer 3 was 0.01 μm, and the porosity of the porous conductive layer 3 was 20%.
The rest is the same as embodiment 3, and is not described herein.
Example 8
Unlike example 3, the thickness of the positive electrode insulating layer 1 and the thickness of the negative electrode insulating layer 2 of the obtained separator were 4 μm and 6 μm, respectively; the thickness of the porous conductive layer 3 was 0.08 μm, and the porosity of the porous conductive layer 3 was 35%.
The rest is the same as embodiment 3, and is not described herein.
Example 9
Unlike example 4, the positive electrode insulating layer 1 was a polyethylene terephthalate film, and the thickness of the positive electrode insulating layer 1 and the thickness of the negative electrode insulating layer 2 of the obtained separator were 7 μm and 9 μm, respectively; the thickness of the porous conductive layer 3 was 1.5 μm, and the porosity of the porous conductive layer 3 was 45%.
The rest is the same as embodiment 4, and the description is omitted here.
Example 10
Unlike example 4, the thickness of the positive electrode insulating layer 1 and the thickness of the negative electrode insulating layer 2 of the obtained separator were 6 μm and 7 μm, respectively; the thickness of the porous conductive layer 3 was 0.3 μm, and the porosity of the porous conductive layer 3 was 55%.
The rest is the same as embodiment 4, and the description is omitted here.
Example 11
As shown in fig. 2 to 3, a lithium ion battery includes an anode 5, a cathode 6, an isolation film and an electrolyte, wherein the anode 5 is manufactured by a conventional manufacturing process, the cathode 6 is a metal lithium cathode, the isolation film is the lithium ion battery diaphragm manufactured in embodiment 1, and a porous conductive layer 3 of the isolation film is electrically connected with a conductive lead to form a diaphragm electrode 7; then, the anode 5, the isolating membrane and the cathode 6 are assembled into a bare cell in a winding or stacking mode, and then the lithium ion battery 4 is prepared through the processes of packaging, injecting liquid (the concentration of lithium salt is 1mol/L), standing, formation, clamp baking, air suction molding, capacity grading and the like.
A method for monitoring short circuit in a battery by using the lithium ion battery comprises the following steps:
firstly, measuring the potential difference between a diaphragm electrode 7 and a negative electrode 6 by a voltage monitor, and recording the measured value as Vm；
In the second step, when Vm approaches zero, it is determined that lithium dendrites have penetrated the negative electrode insulating layer 2 of the separator and come into contact with the porous conductive layer 3, and the battery is about to be short-circuited.
The monitoring principle of the method is as follows: in the process that the lithium dendrite is generated to pierce through the negative electrode insulating layer 2 to the porous conducting layer 3 of the diaphragm, the porous conducting layer 3 and the negative electrode 6 have chemical potential changes, so that the condition of short circuit is monitored by using the obvious potential change, and thus, the electric core can be timely detached or safely processed before the short circuit occurs, so that safety accidents are effectively avoided.
A method for passivating a negative electrode by using the lithium ion battery comprises the following steps:
in the first step, the charging voltage between the positive electrode 5 and the negative electrode 6 is set to V1Charging current is I1In which V is1＞0，I1＞0；
Second step, during charging of the battery, a forward passivation voltage V is applied between the separator electrode 7 and the negative electrode 62And forward passivation current I2In which V is2＞V1，I2＜I1(ii) a During non-battery charging, a forward passivation voltage V is applied between separator electrode 7 and negative electrode 63And forward passivation current I3In which V is3＞0，I3Is greater than 0. By continuously passing a forward passivation current between the separator 7 and the negative electrode 6, lithium ions can be uniformly deposited on the negative electrode 6 at a low current density, and the formation of lithium dendrites is avoided.
A method for supplementing lithium to a battery by applying the lithium ion battery comprises the following steps:
first, in the positiveA reverse voltage V is applied between the electrode 5 and the negative electrode 64In which V is4Less than 0; at the same time, a forward voltage V is applied between the separator 7 and the negative electrode 65In which V is5Is greater than 0. A reverse voltage V is applied between the positive electrode 5 and the negative electrode 64The purpose of this is that the metallic lithium of the negative electrode 6 can replenish the lithium ions to the positive electrode 5 or the electrolytic solution; and a forward voltage V is applied between the diaphragm electrode 7 and the negative electrode 65The purpose of (1) is to avoid deposition of lithium ions on the separator.
In addition, embodiments 12 to 20 of the present invention are different from embodiment 11 in that the lithium ion battery separators prepared in embodiments 2 to 10 are respectively used as the isolation films, and the rest is the same as embodiment 11, and the description is omitted here. Meanwhile, the lithium ion batteries 4 prepared in the embodiments 11 to 20 are sequentially numbered as S1-S10.
Comparative example 1
A lithium ion battery comprises an anode 5, a cathode 6, an isolating membrane and electrolyte, wherein the anode 5 is manufactured by adopting a conventional manufacturing process, the cathode 6 adopts a metal lithium cathode, and the isolating membrane adopts a polypropylene film with the thickness of 16.5 mu m; then assembling the anode 5, the isolating membrane and the cathode 6 into a bare cell in a winding or laminating mode, and then preparing the lithium ion battery through the processes of packaging, injecting liquid (the concentration of lithium salt is 1mol/L), standing, forming, baking by a clamp, air-extracting and forming, grading and the like; and the battery is numbered D1.
Comparative example 2
In contrast to comparative example 1, the preparation of the separator: taking a polypropylene film with the thickness of 8 mu m as a positive electrode insulating layer 1, plating copper on the surface of the polypropylene film by a vacuum evaporation method, wherein the thickness of the polypropylene film is 0.5 mu m, and then taking another polypropylene film with the thickness of 8 mu m as a negative electrode insulating layer 2 of a diaphragm to be hot-pressed on a copper metal layer to obtain the lithium ion battery isolating membrane.
The rest is the same as the comparative example 1 and is not described in detail; and the battery is numbered D2.
The self-discharge rate test, the cycle performance test and the high-temperature storage performance test are respectively carried out on the lithium ion batteries of S1-S10 and D1-D2, and the specific test method comprises the following steps:
self-discharge rate test: mixing lithium ionAfter the cell was fully charged at 25 ℃, it was first allowed to stand at 45 ℃ for 2 days, and the open-circuit voltage OCV of the cell was measured at 25 ℃1(ii) a Then, the battery was left to stand in an environment of 45 ℃ for 3 days, and the open-circuit voltage OCV of the battery was measured at 25 ℃2(ii) a The method for calculating the self-discharge rate comprises the following steps: self-discharge rate K ═ (OCV)1-OCV2) Relative standing time, unit is recorded as mV/h. Generally, a larger value of K indicates a higher self-discharge of the battery. Therefore, the more lithium dendrites generated by the negative electrode during cycling of the battery, the greater the K value exhibited by the battery; especially when lithium dendrites penetrate the separator, the K value increases by orders of magnitude.
And (3) testing the cycle performance: the lithium ion battery is charged at a rate of 0.5C and discharged at a rate of 0.5C at 25 ℃, 400 cycles are sequentially carried out, the capacity of the battery at 0.5C is tested at room temperature, and compared with the room-temperature capacity of the battery before the cycle, the capacity retention rate after the cycle is calculated, and the calculation formula of the capacity retention rate is as follows: capacity retention rate (capacity of battery at 0.5C/room temperature capacity of battery before cycle) × 100%.
And (3) testing the high-temperature storage performance: storing the lithium ion battery at 60 ℃ under 4.2V for 30 days, recording the thickness of the battery before and after storage, and calculating the thickness expansion rate of the battery, wherein the calculation formula is as follows: thickness expansion rate ═ [ (after-storage battery thickness-before-storage battery thickness)/before-storage battery thickness ] × 100%.
The results of the above tests are shown in Table 1.
Table 1: test results of self-discharge performance, cycle performance and high-temperature storage performance of the batteries from S1 to S10 and from D1 to D2
As can be seen from the test results of table 1, the cycle performance and the thickness expansion rate of the lithium ion battery using the separator of the present invention are similar compared to D1, but the self-discharge rate after the cycle is significantly better than D1; therefore, compared with the traditional polyolefin diaphragm, the lithium ion battery diaphragm can effectively inhibit the generation of lithium dendrites on the negative electrode, particularly the lithium metal negative electrode, thereby improving the safety performance of the battery and prolonging the service life of the battery. Compared with D2, the cycle performance, high-temperature storage performance and self-discharge performance of the lithium ion battery are obviously superior to those of D2, because firstly, the transmission of lithium ions is greatly hindered by the isolating membrane with the compact metal layer, so that the cycle performance of the battery is reduced; secondly, the bonding strength of the metal layer arranged between the two insulating substrates is low, and the metal layer is easy to be peeled from the insulating substrates at two sides, so that the thickness expansion rate of the battery is greatly increased; thirdly, the toughness and the electrochemical stability window of the metal layer are inferior to those of the carbon material porous conducting layer, and the penetration force of the metal layer on the insulating layers on two sides is exerted, so that the self-discharge rate of the battery, particularly the self-discharge rate before circulation is larger.
Appropriate changes and modifications to the embodiments described above will become apparent to those skilled in the art from the disclosure and teachings of the foregoing description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (9)
1. The method for passivating the negative electrode of the lithium ion battery comprises a positive electrode, a negative electrode, an isolating film and electrolyte, wherein the isolating film is arranged between the positive electrode and the negative electrode and comprises a positive insulating layer, a negative insulating layer and a porous conducting layer, the porous conducting layer is arranged between the positive insulating layer and the negative insulating layer and is at least one of a graphene layer and a carbon nanotube layer, and the porous conducting layer of the isolating film is electrically connected with a conducting lead to form a diaphragm electrode, and is characterized by comprising the following steps of:
step one, setting the charging voltage between the positive electrode and the negative electrode as V1Charging current is I1In which V is1＞0，I1＞0；
Step two, applying a positive passivation voltage V between the diaphragm electrode and the negative electrode during battery charging2And forward passivation current I2In which V is2＞V1，I2＜I1(ii) a Applying a forward passivation voltage V between the separator and negative electrodes during non-battery charging3And forward passivation current I3In which V is3＞0，I3＞0。
2. The method for passivating the negative electrode of the lithium ion battery according to claim 1, wherein: II said2Less than or equal to 0.05C, said I3≤0.05C。
3. The method for passivating the negative electrode of the lithium ion battery according to claim 1, wherein: the positive insulating layer and the negative insulating layer are at least one of a porous polyolefin film, a polyethylene terephthalate film, a polyvinylidene fluoride film, a polyamide film, a polyimide film and a ceramic film layer.
4. The method for passivating the negative electrode of the lithium ion battery according to claim 1, wherein: the thickness of the porous conducting layer is 0.001-5 mu m.
5. The method for passivating the negative electrode of the lithium ion battery according to claim 4, wherein: the thickness of the porous conducting layer is 0.1-3 mu m.
6. The method for passivating the negative electrode of the lithium ion battery according to claim 1, wherein: the thickness of the positive electrode insulating layer and the thickness of the negative electrode insulating layer are both 1-25 mu m.
7. The method for passivating the negative electrode of the lithium ion battery according to claim 1, wherein: the porosity of the porous conducting layer is 10-85%.
8. The method for passivating the negative electrode of the lithium ion battery according to claim 1, wherein: the cathode material adopted by the cathode is metal lithium.
9. The utility model provides a lithium ion battery mends lithium method to battery, includes anodal, negative pole, sets up barrier film and electrolyte between anodal and negative pole, the barrier film includes anodal insulating layer, negative pole insulating layer and sets up at anodal insulating layer with the porous conducting layer between the negative pole insulating layer, porous conducting layer is at least one kind in graphite alkene layer, carbon nanotube layer, and the porous conducting layer and the electrically conductive lead electric connection of barrier film form the diaphragm utmost point, its characterized in that, includes following step: first, a reverse voltage V is applied between the positive electrode and the negative electrode4In which V is4Less than 0; while applying a forward voltage V between the separator and the negative electrode5In which V is5＞0。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710053775.9A CN106684298B (en) | 2017-01-22 | 2017-01-22 | Application method of lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710053775.9A CN106684298B (en) | 2017-01-22 | 2017-01-22 | Application method of lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106684298A CN106684298A (en) | 2017-05-17 |
| CN106684298B true CN106684298B (en) | 2020-03-31 |
Family
ID=58859107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710053775.9A Active CN106684298B (en) | 2017-01-22 | 2017-01-22 | Application method of lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106684298B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108336437B (en) * | 2017-12-21 | 2020-05-05 | 维沃移动通信有限公司 | Battery detection device and method and mobile terminal |
| CN108321341A (en) * | 2018-03-21 | 2018-07-24 | 闽南师范大学 | A kind of graphene diaphragm of modified lithium battery and its manufacturing method, lithium battery |
| CN108630871B (en) * | 2018-05-16 | 2021-05-28 | 深圳市星源材质科技股份有限公司 | Battery, battery diaphragm and preparation method thereof |
| WO2019231892A1 (en) * | 2018-05-31 | 2019-12-05 | Robert Bosch Gmbh | Electrode configuration with a protrusion inhibiting separator |
| CN109273668B (en) | 2018-09-27 | 2021-04-06 | 宁德新能源科技有限公司 | Negative pole piece and electrochemical device comprising same |
| CN109659475B (en) * | 2018-11-26 | 2021-06-08 | 华南师范大学 | Preparation method of high-performance high-voltage lithium ion battery |
| CN109411682B (en) * | 2018-12-11 | 2022-01-28 | 广东永邦新能源股份有限公司 | High-thermal-stability lithium battery diaphragm and preparation method thereof |
| CN112216875B (en) * | 2019-07-10 | 2022-02-08 | 比亚迪股份有限公司 | Lithium ion battery repeating unit, lithium ion battery, using method of lithium ion battery, battery module and automobile |
| CN110429232A (en) * | 2019-08-14 | 2019-11-08 | 中南大学 | A kind of vast capacity lithium ion battery partition and lithium ion battery |
| CN111508732B (en) * | 2020-04-22 | 2022-04-19 | 东莞东阳光科研发有限公司 | Composite diaphragm for super capacitor and preparation method thereof |
| CN111769331B (en) * | 2020-05-25 | 2021-07-09 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Solid-state battery for controlling ordered growth of lithium dendrites |
| CN115968518A (en) * | 2020-09-14 | 2023-04-14 | 宁德新能源科技有限公司 | Composite solid electrolyte, battery, and electronic device |
| CN112397789B (en) * | 2020-11-17 | 2022-09-27 | 深圳市新威尔电子有限公司 | Three-electrode battery capable of detecting growth of lithium dendrite and method |
| CN114361719A (en) * | 2021-12-08 | 2022-04-15 | 电子科技大学长三角研究院(湖州) | Lithium ion battery diaphragm with potential sensing function |
| CN115377582A (en) * | 2022-08-30 | 2022-11-22 | 华为数字能源技术有限公司 | Battery monomer, battery module, battery package, energy storage system and electric automobile |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100240743B1 (en) * | 1997-07-14 | 2000-01-15 | 성재갑 | Lithium secondary battery using battery separators having conductive coating |
| CN103650203A (en) * | 2011-07-07 | 2014-03-19 | 丰田自动车株式会社 | Secondary battery |
| CN203746941U (en) * | 2013-10-23 | 2014-07-30 | 深圳市冠力新材料有限公司 | Polyethylene diaphragm |
| CN105226226A (en) * | 2015-09-22 | 2016-01-06 | 东莞市爱思普能源科技有限公司 | A kind of lithium ion battery separator and the method with its monitoring battery short circuit |
| CN105702943A (en) * | 2016-01-30 | 2016-06-22 | 山西大学 | Lithium-compensating method for negative electrode material of lithium ion battery |
| CN106025230A (en) * | 2016-07-17 | 2016-10-12 | 中南大学深圳研究院 | Lithium anode for high-specific-energy secondary battery |
-
2017
- 2017-01-22 CN CN201710053775.9A patent/CN106684298B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100240743B1 (en) * | 1997-07-14 | 2000-01-15 | 성재갑 | Lithium secondary battery using battery separators having conductive coating |
| CN103650203A (en) * | 2011-07-07 | 2014-03-19 | 丰田自动车株式会社 | Secondary battery |
| CN203746941U (en) * | 2013-10-23 | 2014-07-30 | 深圳市冠力新材料有限公司 | Polyethylene diaphragm |
| CN105226226A (en) * | 2015-09-22 | 2016-01-06 | 东莞市爱思普能源科技有限公司 | A kind of lithium ion battery separator and the method with its monitoring battery short circuit |
| CN105702943A (en) * | 2016-01-30 | 2016-06-22 | 山西大学 | Lithium-compensating method for negative electrode material of lithium ion battery |
| CN106025230A (en) * | 2016-07-17 | 2016-10-12 | 中南大学深圳研究院 | Lithium anode for high-specific-energy secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106684298A (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106684298B (en) | Application method of lithium ion battery | |
| US11177479B2 (en) | Current collector, electrode plate including the same and electrochemical device | |
| EP3469648B1 (en) | High energy density, high power density, high capacity, and room temperature capable "anode-free" rechargeable batteries | |
| WO2020181681A1 (en) | Hybrid solid-liquid electrolyte lithium storage battery | |
| TWI611443B (en) | Current collector for electrode, positive electrode for non-aqueous electrolytic secondary battery, negative electrode for non-aqueous electrolytic secondary battery, non-aqueous electrolytic secondary battery, electrode for non-aqueous electrolytic elec | |
| CN110112421B (en) | Non-contact mixed solid-liquid electrolyte lithium storage battery and preparation method thereof | |
| US20230134298A1 (en) | Bipolar current collector, electrochemical device, and electronic device | |
| CN111883778A (en) | Lithium ion battery | |
| US20200243841A1 (en) | Anodes, methods for preparing the same, and lithium ion batteries | |
| EP4024503A1 (en) | Lithium secondary battery | |
| US20230136622A1 (en) | Current collector, electrochemical device containing same, and electronic device | |
| CN115377353A (en) | Negative plate and battery using same | |
| CN112490496A (en) | Composite solid electrolyte, preparation method thereof and lithium storage battery | |
| CN113013392B (en) | Electrode plate and preparation method and application thereof | |
| CN117790805A (en) | Bipolar current collector, preparation method thereof, bipolar electrode and lithium battery | |
| CN110120545B (en) | Non-contact mixed solid-liquid electrolyte lithium storage battery and preparation method thereof | |
| CN109962200A (en) | A kind of lithium metal secondary cell | |
| WO2022217559A1 (en) | Negative electrode sheet, preparation method therefor, and secondary battery, battery module, battery pack, and electric apparatus containing same | |
| CN113514520B (en) | Film reference electrode and preparation method thereof | |
| CN114843640A (en) | Lithium ion battery reference electrode and preparation method and application thereof | |
| CN112259706A (en) | Pre-lithiation pole piece, preparation method of pre-lithiation pole piece and lithium ion battery | |
| CN218513485U (en) | Current collector for lithium ion battery and lithium ion battery comprising same | |
| CN217740572U (en) | Three-dimensional support metal lithium cathode | |
| EP4194589B1 (en) | Copper plating solution and negative electrode composite current collector prepared using same | |
| WO2022027550A1 (en) | Polymer current collector, preparation method therefor, and secondary battery, battery module, battery pack, and apparatus related thereto |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Hu Haibo Inventor after: Wen Baohua Inventor after: Chen Zhen Inventor after: Tao Zhe Inventor after: Wang Zhibin Inventor after: Liu Keyong Inventor after: Liu Kai Inventor after: Liu Xi Inventor before: Hu Haibo Inventor before: Wen Baohua Inventor before: Chen Zhen Inventor before: Tao Zhe Inventor before: Liu Zhibin Inventor before: Liu Keyong Inventor before: Liu Kai Inventor before: Liu Xi |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: An application method of lithium ion battery Effective date of registration: 20210729 Granted publication date: 20200331 Pledgee: Bank of Changsha Co.,Ltd. Zhuzhou branch Pledgor: HUNAN LIFANG NEW ENERGY SCIENCE & TECHNOLOGY Co.,Ltd. Registration number: Y2021980007086 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230208 Granted publication date: 20200331 Pledgee: Bank of Changsha Co.,Ltd. Zhuzhou branch Pledgor: HUNAN LIFANG NEW ENERGY SCIENCE & TECHNOLOGY Co.,Ltd. Registration number: Y2021980007086 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Application method of a lithium-ion battery Effective date of registration: 20230829 Granted publication date: 20200331 Pledgee: Agricultural Bank of China Limited Zhuzhou branch Pledgor: HUNAN LIFANG NEW ENERGY SCIENCE & TECHNOLOGY Co.,Ltd. Registration number: Y2023980054119 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |