CN115939308A - Lithium-supplement positive pole piece, preparation method thereof and lithium ion battery - Google Patents
Lithium-supplement positive pole piece, preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN115939308A CN115939308A CN202211651828.4A CN202211651828A CN115939308A CN 115939308 A CN115939308 A CN 115939308A CN 202211651828 A CN202211651828 A CN 202211651828A CN 115939308 A CN115939308 A CN 115939308A
- Authority
- CN
- China
- Prior art keywords
- lithium
- positive
- active material
- lithium supplement
- positive electrode
- 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.)
- Pending
Links
- 239000013589 supplement Substances 0.000 title claims abstract description 145
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 170
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 170
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 117
- 239000007774 positive electrode material Substances 0.000 claims abstract description 98
- 239000002002 slurry Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 29
- 239000006258 conductive agent Substances 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000007765 extrusion coating Methods 0.000 claims description 6
- 238000013461 design Methods 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 4
- 229910018071 Li 2 O 2 Inorganic materials 0.000 claims description 4
- 229910018091 Li 2 S Inorganic materials 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 239000011888 foil Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000013543 active substance Substances 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium supplement positive pole piece, a preparation method thereof and a lithium ion battery. In the invention, the single lithium supplement reagent layer is distributed in a direction vertical to the width direction of the current collector, so that the electronic conduction between the positive active material layer and the current collector is not influenced, and the transmission path of lithium ions is not deteriorated.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a lithium supplement positive pole piece, a preparation method thereof and a lithium ion battery.
Background
In order to meet the requirements of electric vehicles and large-scale energy storage, the next-generation power battery needs higher energy density, the next-generation energy storage battery has higher cycle life, and the technology capable of simultaneously improving the energy density and the cycle life of the battery at present is a lithium supplement technology.
The lithium supplement technology mainly comprises a negative electrode electrochemical method, a negative electrode chemical method and a positive electrode pre-lithiation method.
The negative electrode electrochemical method is mainly characterized in that before the battery is assembled, a negative electrode, a lithium source and electrolyte form a battery, the negative electrode is charged, a certain amount of lithium ions are stored in the negative electrode in advance, and then the negative electrode and a corresponding positive electrode material are assembled into a full battery. The method relates to the problem of battery assembly after disassembly, so that the whole operation is complex, the process cost is high, and the method is not suitable for mass production.
Currently, the most studied method is a negative electrode chemical method, that is, a negative electrode material and metallic lithium or other low-potential lithium-containing chemical reagents are subjected to redox reaction to make up for the loss of lithium. In the environment of the electrolyte, the lithium ion flow moves directionally due to the potential difference between the metal lithium and the negative electrode material, wherein the lithium ions generated by the lithium foil are released into the electrolyte, and in order to keep the charge conservation, the lithium ions in the electrolyte are inserted into the negative electrode or have redox reaction with the negative electrode, so that the pre-lithiation of the negative electrode is completed. Although the technical scheme is simple in process and high in lithium supplementing efficiency, the capacity of metal lithium is very high, the surface capacity of a lithium source is far higher than the actually required active lithium ion capacity due to technical limitation, and in addition, lithium foils and other lithium-containing reagents with low potential are high in activity, easily react with water, air and other gases in the air, have very large potential safety hazards and are difficult to be compatible with the existing assembly process.
Recently, the positive electrode prelithiation method attracts the attention of many researchers, in which a positive electrode prelithiation reagent is added to a positive electrode material, and when the positive electrode prelithiation reagent is charged for the first time, the prelithiation reagent with high lithium ion content in the molecule irreversibly removes active lithium ions to compensate for the first irreversible lithium consumption of a negative electrode material, so that the energy density of a battery is improved; the anode prelithiation reagent can be blended with an anode material by the existing production process, the lithium supplement capacity can be accurately controlled according to the addition content, and the safety is high. Because the process is simple and perfectly compatible with the existing battery process, the energy density of the full battery can be effectively improved, the capacity of the pre-lithiated lithium ions can be accurately controlled, and the large-scale commercial application is very facilitated.
At present, the common scheme of anode lithium supplement is to blend a lithium supplement reagent and an anode material at the stage of material mixing and slurry homogenizing, and make up for the consumption of active lithium ions of a battery cell by using redundant lithium ions which are separated out when the lithium supplement reagent is charged for the first time, so that the energy density of the battery cell is improved, and the cycle life of the battery cell is prolonged. However, most positive electrode lithium-supplementing agents have a problem of poor conductivity, such as Li 2 S、Li 2 O、Li 2 O 2 、LiF、Li 5 FeO 4 、Li 2 NiO 2 It must be combined with a higher proportion of conductive agent to effectively remove the lithium ions it contains. The positive electrode lithium supplement reagent is simply blended with the positive electrode active material, the lithium ions firstly extracted by the lithium supplement reagent are lower than the theoretical capacity; in addition, because of the low-conductivity substances remained after the lithium supplement reagent removes lithium, the resistance of the positive pole piece is increased, the exertion of gram capacity of the positive active substance is deteriorated, and finally, the energy density of the battery cell is not ideal to be improved, and the cycle life of the battery cell is deteriorated. In addition, CN 107068972A coats the lithium supplement material layer on the surface of the positive electrode material layer, although the ratio of the positive electrode material, the lithium supplement material and the conductive agent can be respectively adjusted to improve the capacity exertion of the lithium supplement reagent, the lithium supplement material layer coated on the surface of the positive electrode material can hinder the conduction of lithium ions, increase the transmission distance of the positive electrode material lithium ions into the negative electrode material, cause concentration polarization during charging and discharging, and deteriorate the electrochemical performance of the battery cell; meanwhile, CN109686947A directly arranges a lithium supplement layer on the surface of the current collector, which can avoid the lithium supplement layer from deteriorating the lithium ion conduction, but because the common inorganic lithium supplement material has poor electrical conductivity, the electron conduction rate is deteriorated, the physical internal resistance of the battery is increased, and the two methods need to carry out multiple coating, thus increasing the process cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a lithium supplement positive pole piece and a preparation method thereof and a lithium ion battery, wherein a positive active material and a lithium supplement agent are separately homogenized, different conductive agent contents are matched according to respective electronic conduction characteristics, and then the two kinds of slurry are coated on a positive current collector at one time through extrusion coating; the lithium supplement material is longitudinally distributed (vertical to the width direction of the current collector), so that the electronic conduction of the positive electrode material layer is not influenced, the transmission path of lithium ions is not deteriorated, and meanwhile, because the lithium supplement layer has high conductive agent content and high porosity, more electrolyte is contained in the longitudinal lithium supplement material layer, so that the lithium ions of the positive electrode material can be rapidly removed through the electrolyte in the lithium supplement layer, and the concentration polarization during rapid charging and discharging is improved; therefore, the method not only enables the respective performances of the positive active material and the lithium supplement agent to be exerted to the maximum without influencing each other, but also maximizes the effect of the lithium supplement agent, improves the energy density of the battery cell and prolongs the cycle life of the battery cell; meanwhile, the process is simple, the design can be flexibly carried out according to the demand of lithium supplement amount, the coating of the anode material and the lithium supplement reagent can be completed at one time, and the processing cost is low.
In order to achieve the above object, the present invention adopts the following technical solutions.
The utility model provides a mend lithium positive pole piece, positive pole piece includes the anodal mass flow body, coating positive active material layer and mends lithium reagent layer on the anodal mass flow body, wherein, the list mend lithium reagent layer and list positive active material layer all lays along mass flow body length direction, mend lithium reagent layer with positive active material layer is in along mass flow body width direction interval arrangement on the mass flow body surface.
In the above-described lithium replenishment positive electrode sheet, as a preferred embodiment, the number of the lithium replenishment reagent layers is adjusted in accordance with the actual amount of lithium replenishment, and the number of the lithium replenishment reagent layers may be 1 to 5 (e.g., 2, 3, 4) and the width of the lithium replenishment reagent layer may be 0.5mm to 30mm (e.g., 1mm, 5mm, 10mm, 15mm, 20mm, 25 mm).
In the above lithium-supplement positive electrode sheet, as a preferred embodiment, the lithium supplement reagent layer includes a lithium supplement reagent, a first conductive agent, and a first binder.
In the above lithium-supplement positive electrode sheet, as a preferred embodiment, in the lithium supplement reagent layer, the lithium supplement reagent includes Li 2 S、Li 2 O、Li 2 O 2 、LiF、Li 1+a1 FeO 4 (0<a 1 ≤5)，Li 1+a2 NiO 2 (0<a 2 ≤3)，Li 1+a3 Ni x Co y Mn z O 2 (0<a 3 3,0 and 1,0 and 1,0 and z 1, and x + y + z = 1).
In the lithium supplement positive pole piece, as a preferred embodiment, the mass ratio of the lithium supplement reagent, the first conductive agent and the first binder in the lithium supplement reagent layer is 60-95 (e.g., 65, 70, 80, 85, 88): 2-30 (e.g., 5, 10, 15, 20, 25, 28): 2-15 (e.g., 3, 5, 10, 12, 14), and the sum of the ratios is equal to 100.
In a preferred embodiment of the lithium supplement positive electrode sheet, the thickness of the lithium supplement reagent layer is equal to or 1 μm to 20 μm (e.g., 3 μm, 5 μm, 10 μm, 15 μm, 18 μm) lower than the thickness of the positive electrode active material.
According to the invention, the thickness of the lithium supplement reagent layer which is the same as or lower than that of the positive active material is adopted, and particularly the thickness of the lithium supplement reagent layer which is lower than that of the positive active material is adopted, so that the liquid retention rate of the positive pole piece is improved, the concentration polarization of the positive pole is improved, and the discharge capacity and the rate capability of the positive pole are improved.
As a preferred embodiment, the positive active material layer and the lithium supplement reagent layer may be coated on either one or both surfaces of the positive current collector.
In a preferred embodiment of the lithium supplement positive electrode sheet, the lithium supplement reagent layer has 2 to 4 (e.g., 3) strips and a width of 1 to 10mm (e.g., 1mm, 3mm, 5mm, 6mm, 7mm, 8mm, 9 mm).
In the above lithium-doped positive electrode sheet, as a preferred embodiment, the positive electrode active material layer contains a positive electrode active material, a second conductive agent, and a second binder; wherein, in the positive electrode active material layer, the positive electrode active material is 90 to 98% (e.g., 92%, 94%, 95%, 97%), the second conductive agent is 0.5 to 5% (e.g., 1%, 2%, 3%, 4%), and the second binder is 0.5 to 5% (e.g., 1%, 2%, 3%, 4%) by mass.
As a preferred embodiment, in the lithium supplement positive electrode sheet, the mass ratio of the positive electrode active material layer to the lithium supplement reagent layer is (90-99): 1-10 (for example, 92, 94, 95, 5, 96, 4, 97, 98.
In the above lithium-complementary positive electrode sheet, as a preferred embodiment, in the positive electrode active material layer, the positive electrode active material includes a ternary positive electrode material Li x M y O 2 (x is 1-2,y is 1-2), lithium cobaltate, lithium manganate, lithium iron phosphate, lithium iron manganese phosphate (LiMn) z Fe 1-z PO 4 And z is 0.2-0.8), or a doped positive electrode material of the materials, wherein M comprises one or more of Ni, mn, co, al, mg and Zr.
In the above lithium-supplementing positive electrode sheet, as a preferred embodiment, the first binder or the second binder includes one or a combination of more of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, lithium polyacrylate, sodium polyacrylate, carboxymethyl cellulose, and styrene butadiene rubber.
As a preferred embodiment, the first conductive agent or the second conductive agent includes at least one of conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, graphene, metal powder, or carbon fiber.
The invention also provides a preparation method of the lithium-supplement positive pole piece, and the following technical scheme is adopted.
The preparation method of the lithium-supplement positive pole piece comprises the following steps:
(1) Preparation of positive electrode active material layer slurry
Adding the positive active material, a second conductive agent and a second binder into a second solvent according to the formula, and fully stirring to obtain positive active material layer slurry;
(2) Preparation of lithium supplement reagent layer slurry
Adding the lithium supplement reagent, the first conductive agent and the first binder into the first solvent according to the formula, and fully stirring to obtain active slurry of the positive electrode lithium supplement reagent;
(3) Preparation of lithium-supplement positive pole piece
And coating the positive active material layer slurry and the lithium supplement reagent layer slurry on the surface of any one side or two sides of the positive current collector at one time according to the design requirement of the lithium supplement positive pole piece to obtain the lithium supplement positive pole piece.
In the above preparation method of the lithium-supplement positive electrode piece, as a preferred embodiment, in the step (3), the positive active material layer slurry and the lithium-supplement reagent layer slurry are coated on any one side or both sides of the positive current collector at a time by using a conventional extrusion coating machine and a designed extrusion gasket, so as to obtain the lithium-supplement positive electrode piece.
In the above method for preparing a lithium-complementary positive electrode plate, as a preferred embodiment, in the step (3), after the positive electrode active material layer and the lithium-complementary reagent layer are coated on one side of the positive electrode current collector, the positive electrode active material layer and the lithium-complementary reagent layer are further coated on the other side of the positive electrode current collector.
In the above method for preparing a lithium-supplement positive electrode plate, as a preferred embodiment, the step (3) further includes drying, cold pressing, slitting, and cutting after the coating is completed, so as to obtain the positive electrode plate.
In the above method for preparing a lithium-doped positive electrode sheet, as a preferred embodiment, in the step (1) or (2), the stirring is performed in a vacuum stirrer.
Because most positive electrode lithium-supplementing agents have the problem of poor conductivity, such as Li 2 S、Li 2 O、Li 2 O 2 、LiF、Li 5 FeO 4 、Li 2 NiO 2 It must be combined with a higher proportion of conductive agent to effectively remove the lithium ions it contains. Simply adding a lithium-adding reagent to the positive electrode and a positive electrode active materialThe materials are blended, and the lithium ions extracted by the lithium supplement reagent are lower than the theoretical capacity; in addition, because of the low-conductivity substances remained after the lithium supplement reagent removes lithium, the resistance of the positive pole piece is increased, the exertion of gram capacity of the positive active substance is deteriorated, and finally the improvement of the energy density of the battery cell is not ideal. Therefore, the invention separates the positive active material and the lithium supplement agent into uniform slurry, matches different formulas according to respective characteristics, and then coats (coats) the two slurries on one side surface of the positive current collector by extrusion coating at one time. The method not only enables respective performances of the positive active material and the lithium supplement agent to be exerted to the maximum without mutual influence, but also maximizes the effect of the lithium supplement agent, and improves the energy density and cycle life of the battery cell; meanwhile, the process is simple, the design can be flexibly carried out according to different lithium supplement amounts, the coating of the anode material and the lithium supplement reagent on the surface of one side of the anode current collector can be completed at one time, and the processing cost is low.
In the invention, in the step (3), after the positive electrode active material layer slurry or the lithium supplement reagent layer slurry is coated on one side or both sides of the positive electrode current collector, the lithium supplement reagent layer slurry or the positive electrode active material layer slurry is coated on one side or both sides of the positive electrode current collector, so as to obtain the lithium supplement positive electrode piece; that is, a method of coating the positive electrode active material layer slurry or the lithium replenishment reagent layer slurry on one side or both sides of the positive electrode current collector is adopted.
The invention also provides a lithium ion battery which comprises a positive pole piece, an isolating membrane and a negative pole piece, wherein the positive pole piece adopts the lithium-supplement positive pole piece.
In the invention, the technical characteristics can be freely combined to form a new technical scheme under the condition of not conflicting with each other.
Compared with the prior art, the invention has the following beneficial technical effects:
1. according to the invention, the positive active substance and the lithium supplement reagent are separated and homogenized, different conductive agent contents are matched according to respective electronic conduction characteristics, and then the two slurries are coated on the surface of one side of the positive current collector at one time through extrusion coating, so that the respective performances of the positive active substance and the lithium supplement reagent are maximized and are not influenced with each other, the effect of the lithium supplement reagent is maximized, the energy density of a battery cell is improved, and the cycle life of the battery cell is prolonged;
2. the single lithium supplement reagent layer is longitudinally distributed (perpendicular to the width direction of the current collector, namely, distributed along the length direction of the current collector), so that the electronic conduction between the positive active material layer and the current collector is not influenced, and the transmission path of lithium ions is not deteriorated;
3. the preparation process of the lithium-supplement positive pole piece is simple, the design can be flexibly carried out according to different lithium supplement amounts, the coating of the positive active material layer and the lithium supplement reagent layer on the surface of one side of the positive current collector can be completed at one time, and the processing cost is low.
Drawings
Fig. 1 is a cross-sectional view of a positive electrode sheet of the present invention taken along the width of the current collector;
FIG. 2 is a top view of the positive plate of the present invention;
fig. 3 is a schematic diagram of a combination of positive and negative electrode plates and a separator of a lithium ion battery (i.e., a battery cell) according to the present invention;
description of reference numerals: 1 is a current collector; 2 is a lithium supplement reagent layer; 3 is a positive electrode active material layer; 4 is a diaphragm; 5 is a negative pole piece.
Detailed Description
The present invention will be described in detail with reference to examples. The various examples are provided by way of explanation of the invention, and not limitation of the invention. In fact, it will be apparent to those skilled in the art that modifications and variations can be made in the present invention without departing from the scope or spirit thereof. For instance, features illustrated or described as part of one embodiment, can be used with another embodiment to yield a still further embodiment. It is therefore intended that the present invention encompass such modifications and variations as fall within the scope of the appended claims and equivalents thereof.
In the present invention, the reagents and materials are commercially available, unless otherwise specified. In the present invention, the portions not described in detail may adopt the conventional technical solutions in the field.
Mend lithium positive pole piece's cross-sectional view and top view in fig. 1-2, a mend lithium positive pole piece, including positive current collector 1, coating mends lithium reagent layer 2 and positive active material layer 3 on positive current collector surface, wherein, single bar is mended lithium reagent layer and single bar positive active material layer and is all laid along current collector length direction, the length direction on the benefit lithium reagent layer that forms on the current collector surface and positive active material layer is unanimous with the length direction of current collector, mend lithium reagent layer and positive active material layer and arrange along current collector width direction interval on the current collector surface, include on a current collector promptly that many current collectors lay along length direction mends lithium reagent layer and many positive active material layers, many mend lithium reagent layer and many positive active material layers along current collector width direction NULL.
As shown in fig. 3, a lithium ion battery (i.e., a battery cell) includes a positive electrode plate, a separator 4, and a negative electrode plate 5, where the positive electrode plate includes a positive electrode current collector 1, a lithium supplement reagent layer 2 coated on the surface of the positive electrode current collector, and a positive electrode active material layer 3.
Example 1
Preparation of positive pole piece
The anode active material LiFePO is added 4 Fully stirring the conductive carbon black Super-P and the PVDF binder in a solvent system of N-methylpyrrolidone (NMP) by a vacuum stirrer according to a weight ratio of 97.3;
adding a lithium supplement reagent, conductive carbon black and polyvinylidene fluoride (PVDF) into an N-methylpyrrolidone NMP solvent according to a formula, and fully stirring to obtain lithium supplement reagent layer slurry; in the dried positive pole piece, the lithium supplement reagent layer accounts for 4% of the total weight of the positive active material layer and the lithium supplement reagent layer (namely, the adding proportion of the lithium supplement reagent layer); see table 1 for details;
as shown in fig. 1, the positive electrode slurry and the lithium supplement reagent layer slurry are coated on any one side of an Al foil substrate with a thickness of 12 μm at a time by a conventional extrusion coater and a designed extrusion shim, and then coated on the other side of the Al foil substrate with a thickness of 12 μm at a time after drying, and then dried, cold-pressed, striped, and cut to obtain a positive electrode sheet. Wherein the number of the positive electrode active material layers is 3, each positive electrode active material layer has a width of 20mm and a thickness of 186 μm; the number of lithium supplement reagent layers was 2, each having a width of 1.3mm and a thickness of 186. Mu.m.
Preparation of negative pole piece
Dissolving the negative electrode active material (95% by weight of graphite +5% by weight of silicon carbon), a conductive agent, styrene-butadiene rubber and sodium carboxymethyl cellulose (binder) in deionized water according to a weight ratio of 96.5;
coating the negative electrode slurry containing the negative electrode active material and the heat conduction slurry on the surface of a Cu foil with the thickness of 6 mu m of a negative electrode current collector through a specially designed extrusion coating machine, drying, cold pressing and cutting sequentially to obtain the negative electrode piece with the double-layer active material layer, wherein the thickness of the negative electrode piece after cold pressing is 130 mu m.
Preparation of the electrolyte
Mixing Ethylene Carbonate (EC), ethyl Methyl Carbonate (EMC), and dimethyl carbonate (DMC) at a volume ratio of 3 6 Dissolving the mixture in mixed organic solvent to prepare LiPF 6 Electrolyte with concentration of 1 mol/L.
Preparation of the separator
The base material of the isolation film is Polyethylene (PE) with the thickness of 8 μm, two sides of the base material of the isolation film are respectively coated with an alumina ceramic layer with the thickness of 2 μm, and finally, two sides coated with the ceramic layer are respectively coated with polyvinylidene fluoride (PVDF) adhesive with the thickness of 2.5mg, and the base material of the isolation film is dried.
Preparation of lithium ion secondary battery
Stacking the positive pole piece, the isolating film and the negative pole piece in sequence to enable the isolating film to be positioned between the positive pole piece and the negative pole piece to play an isolating role, and then winding to obtain a bare cell; welding a qualified bare cell on a top cover through a tab, placing the qualified bare cell in an outer packaging shell, drying the bare cell, injecting electrolyte, and performing vacuum packaging, standing, formation, shaping and other processes to obtain the soft-package lithium ion secondary battery with the capacity of about 5000mAh.
Example 2
Example 2 differs from example 1 in that the positive electrode active material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 The lithium supplement reagent layer accounts for 3% of the total mass of the positive active material layer and the lithium supplement reagent layer (namely, the adding proportion of the lithium supplement reagent layer); the mass ratio of the positive electrode active material to the conductive carbon black to the polyvinylidene fluoride is 97.6.
In the positive electrode plate prepared in this embodiment, the number of positive electrode active material layers is 3, each positive electrode active material layer has a width of 20mm and a thickness of 110 μm; the number of lithium supplement reagent layers was 2, each layer had a width of 1mm and a thickness of 110 μm.
Example 3
The embodiment 3 is different from the embodiment 1 in that, in the lithium supplement reagent layer, the mass ratio of the lithium supplement reagent, the conductive carbon black and the polyvinylidene fluoride is 95.
In the positive electrode plate prepared in this example, the number of positive active material layers is 3, each positive active material layer has a width of 20mm and a thickness of 186 μm; the number of lithium supplement reagent layers was 2, each having a width of 1.3mm and a thickness of 186. Mu.m.
Example 4
Example 4 differs from example 1 in that the lithium supplement reagent layer accounts for 3% of the total weight of the positive electrode active material layer and the lithium supplement reagent layer; see table 1 for details.
In the positive electrode plate prepared in this example, the number of positive electrode active material layers is 3, each positive electrode active material layer has a width of 20mm and a thickness of 186 μm; the number of lithium supplement reagent layers was 2, each width was 1.0mm, and the thickness was 186. Mu.m. The other technical means are the same as those in embodiment 1.
Example 5
Example 5 differs from example 4 in that the lithium supplementing agent is Li 2 NiO 2 The mass ratio of the lithium supplement reagent, the conductive carbon black and the polyvinylidene fluoride is 90.
In the positive electrode plate prepared in this example, the number of positive active material layers is 3, each positive active material layer has a width of 20mm and a thickness of 186 μm; the number of the lithium supplement reagent layers is 2, the width of each lithium supplement reagent layer is 1.5mm, and the thickness of each lithium supplement reagent layer is 110 mu m;
comparative example 1
The difference between the comparative example and the example 1 is that in the comparative example, the positive pole piece does not contain a lithium supplement reagent layer. In particular, the amount of the solvent to be used,
preparation of positive pole piece
Mixing the anode active material LiFePO 4 Fully stirring the conductive carbon black Super-P and the PVDF binder in a solvent system of N-methylpyrrolidone and NMP by a vacuum stirrer according to the weight ratio of 97.3; and coating the positive electrode slurry on two surfaces of an Al foil substrate with the thickness of 12 microns, and sequentially drying, cold pressing, slitting and cutting to obtain a positive electrode piece.
In the positive pole piece prepared by the comparative example, the positive active material layer is tiled on the two side surfaces of the positive current collector, and the thickness is 186 μm.
Comparative example 2
The present comparative example is different from example 2 in that the positive electrode sheet does not include a lithium supplement reagent layer therein, and the positive electrode slurry is coated on both surfaces of a 12 μm thick Al foil substrate to form a positive electrode sheet having positive electrode active material layers laid flat on both side surfaces of the Al foil substrate.
In the positive electrode plate prepared in the comparative example, the positive active material layer is tiled on the two side surfaces of the positive current collector, and the thickness is 110 μm.
Comparative example 3
The comparative example is different from example 1 in that the coating manner of the positive electrode active material layer and the lithium supplement reagent layer on the surface of the positive electrode current collector is different, and the lithium supplement reagent layer and the positive electrode active material layer are stacked in the height or thickness direction of the positive electrode current collector. Specifically, the method comprises the following steps:
coating the positive active material slurry on two surfaces of an Al foil substrate with the thickness of 12 microns to obtain a positive current collector with two side surfaces containing a positive active material layer, coating a lithium supplement reagent layer slurry on the surface of the positive active material layer after drying, and obtaining a positive pole piece with two side surfaces of the current collector coated with the positive active material layer and the lithium supplement reagent layer in sequence through drying, cold pressing, stripping and cutting.
In the comparative example, the thickness of the positive active material layer of the obtained positive electrode piece was 186 μm, and the thickness of the lithium supplement reagent layer was 8 μm.
Comparative example 4
The comparative example is different from example 1 in that the coating manner of the positive electrode active material layer and the lithium supplement reagent layer on the surface of the positive electrode current collector is different, and the lithium supplement reagent layer and the positive electrode active material layer are stacked in the height or thickness direction of the positive electrode current collector. Specifically, the method comprises the following steps:
coating the slurry of the lithium supplement reagent layer on two surfaces of a 12-micron-thick Al foil substrate to obtain a positive electrode current collector with the surfaces of the two sides containing the lithium supplement reagent layer, coating the slurry of the positive electrode active substance on the surface of the lithium supplement reagent layer after drying, and obtaining a positive electrode piece with the surfaces of the two sides of the positive electrode current collector coated with the lithium supplement reagent layer and the positive electrode active substance layer in sequence through drying, cold pressing, slitting and cutting.
In the comparative example, the thickness of the positive active material layer of the obtained positive pole piece is 186 μm; the thickness of the lithium supplement reagent layer is 8 μm.
Electrochemical performance testing of batteries
Discharging the battery to 2.75V at the temperature of 25 ℃, standing for 1 hour, charging the battery to 4.2V at the temperature of 1C, standing for 1 hour, then discharging the battery to 2.75V at the temperature of 1C, detecting the 1C discharge capacity (namely the capacity at the first circulation), and calculating the capacity retention rate by dividing the capacity after 500 cycles by the capacity at the first circulation; charging at a rate of 0.33C followed by discharging at a rate of 0.33C, multiplying the average voltage by the capacity at the time of discharge yields a 0.33C energy density. Table 1 shows the main process parameters and electrochemical properties of examples 1-5 and comparative examples 1-4.
TABLE 1 Main Process parameters and electrochemical Properties in examples 1-5 and comparative examples 1-4
Claims (10)
1. The lithium supplement positive pole piece is characterized by comprising a positive current collector, a positive active material layer and a lithium supplement reagent layer, wherein the positive active material layer and the lithium supplement reagent layer are coated on the positive current collector, the lithium supplement reagent layer and the positive active material layer are arranged along the length direction of the current collector, and the lithium supplement reagent layer and the positive active material layer are arranged on the surface of the current collector at intervals along the width direction of the current collector.
2. The lithium supplement positive pole piece of claim 1, wherein the number of the lithium supplement reagent layers is adjusted according to the actual lithium supplement amount, the number of the lithium supplement reagent layers is 1-5, and the width of the lithium supplement reagent layer is 0.5mm-30mm; and/or the presence of a gas in the gas,
the positive electrode active material layer and the lithium supplement reagent layer may be coated on either one or both surfaces of the positive electrode current collector.
3. The lithium supplement positive pole piece of claim 1 or 2, wherein the lithium supplement reagent layer comprises a lithium supplement reagent, a first conductive agent and a first binder; the positive electrode active material layer contains a positive electrode active material, a second conductive agent and a second binder;
in the lithium supplement reagent layer, the lithium supplement reagent comprises Li 2 S、Li 2 O、Li 2 O 2 、LiF、Li 1+a1 FeO 4 (0<a 1 ≤5)，Li 1+a2 NiO 2 (0<a 2 ≤3)，Li 1+a3 Ni x Co y Mn z O 2 (0<a 3 3,0 and 1,0 and 1,0 and z 1, and x + y + z = 1); and/or the presence of a gas in the atmosphere,
in the positive electrode active material layer, the positive electrode active material includes a ternary positive electrode material Li x M y O 2 One or more of lithium cobaltate, lithium manganate, lithium iron phosphate and lithium iron manganese phosphate, or a doped positive electrode material of the above materials, wherein M comprises Ni, mn, co, al, mg and Zr, x is 1-2,y and is 1-2; and/or the presence of a gas in the atmosphere,
the first binder or the second binder comprises one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylic acid, lithium polyacrylate, sodium polyacrylate, carboxymethyl cellulose and styrene butadiene rubber; and/or the presence of a gas in the gas,
the first conductive agent or the second conductive agent includes at least one of conductive carbon black, acetylene black, ketjen black, conductive graphite, conductive carbon fiber, carbon nanotube, graphene, metal powder, or carbon fiber.
4. The lithium-supplementing positive electrode sheet according to claim 3,
in the lithium supplement reagent layer, the mass ratio of the lithium supplement reagent to the first conductive agent to the first binder is (60-95); and/or the presence of a gas in the gas,
in the positive active material layer, the positive active material is 90-98 wt%, the second conductive agent is 0.5-5wt%, and the second binder is 0.5-5wt%; and/or the presence of a gas in the gas,
the mass ratio of the positive active material layer to the lithium supplement reagent layer is (90-99) to (1-10).
5. The lithium-supplementing positive pole piece of claim 2, wherein the lithium-supplementing reagent layer has 2 to 4 strips and a width of 1 to 10mm.
6. The lithium supplement positive pole piece according to claim 1 or 2, wherein the thickness of the lithium supplement reagent layer is the same as or 1 μm to 20 μm lower than that of the positive active material.
7. The preparation method of the lithium-supplementing positive pole piece according to any one of claims 1 to 6, characterized by comprising the following steps:
(1) Preparation of positive electrode active material layer slurry
Adding the positive active material, a second conductive agent and a second binder into a second solvent according to the formula, and fully stirring to obtain positive active material layer slurry;
(2) Preparation of lithium supplement reagent layer slurry
Adding the lithium supplementing reagent, the first conductive agent and the first binder into the first solvent according to the formula, and fully stirring to obtain active slurry of the positive electrode lithium supplementing reagent;
(3) Preparation of lithium-supplement positive pole piece
And coating the positive active material layer slurry and the lithium supplement reagent layer slurry on the surface of any one side or two sides of the positive current collector at one time according to the design requirement of the lithium supplement positive pole piece to obtain the lithium supplement positive pole piece.
8. The method for preparing the lithium-supplementing positive electrode piece according to claim 7,
in the step (1) or (2), the stirring is performed in a vacuum stirrer; and/or the presence of a gas in the gas,
and (4) in the step (3), coating the positive active material layer slurry and the lithium supplement reagent layer slurry on the surface of any one side or two sides of the positive current collector at one time through an extrusion coating machine and a designed extrusion gasket to obtain the lithium supplement positive pole piece.
9. The method for preparing a lithium-supplementing positive electrode sheet according to claim 7 or 8,
and (4) after the coating is finished, drying, cold pressing, splitting and cutting are further carried out in the step (3), so that the positive pole piece is obtained.
10. A lithium ion battery is characterized by comprising a positive pole piece, a separation film and a negative pole piece, wherein the positive pole piece adopts the lithium-supplementing positive pole piece of any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211651828.4A CN115939308A (en) | 2022-12-21 | 2022-12-21 | Lithium-supplement positive pole piece, preparation method thereof and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211651828.4A CN115939308A (en) | 2022-12-21 | 2022-12-21 | Lithium-supplement positive pole piece, preparation method thereof and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115939308A true CN115939308A (en) | 2023-04-07 |
Family
ID=86652254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211651828.4A Pending CN115939308A (en) | 2022-12-21 | 2022-12-21 | Lithium-supplement positive pole piece, preparation method thereof and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115939308A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116344979A (en) * | 2023-05-29 | 2023-06-27 | 江苏正力新能电池技术有限公司 | Positive electrode plate and preparation method and application thereof |
| CN116705981A (en) * | 2023-07-27 | 2023-09-05 | 宁德时代新能源科技股份有限公司 | Negative electrode plate, preparation method thereof, battery and electric equipment |
-
2022
- 2022-12-21 CN CN202211651828.4A patent/CN115939308A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116344979A (en) * | 2023-05-29 | 2023-06-27 | 江苏正力新能电池技术有限公司 | Positive electrode plate and preparation method and application thereof |
| CN116344979B (en) * | 2023-05-29 | 2023-08-11 | 江苏正力新能电池技术有限公司 | Positive electrode plate and preparation method and application thereof |
| CN116705981A (en) * | 2023-07-27 | 2023-09-05 | 宁德时代新能源科技股份有限公司 | Negative electrode plate, preparation method thereof, battery and electric equipment |
| CN116705981B (en) * | 2023-07-27 | 2024-05-03 | 宁德时代新能源科技股份有限公司 | Negative electrode plate, preparation method thereof, battery and electric equipment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105958008B (en) | A kind of lithium ion battery anode composite piece, preparation method and lithium ion battery | |
| CN102956895B (en) | Positive electrode that surface recombination is coated and preparation method thereof and lithium ion battery | |
| CN110707287B (en) | Metal lithium negative electrode, preparation method thereof and lithium battery | |
| CN107768743A (en) | A kind of lithium ion battery mends lithium method | |
| CN110581253A (en) | Electrode pole piece, preparation method thereof and solid-state battery | |
| CN115939308A (en) | Lithium-supplement positive pole piece, preparation method thereof and lithium ion battery | |
| CN109037659A (en) | A kind of preparation method of bilayer carbon-coated LiFePO 4 for lithium ion batteries material | |
| CN110676433B (en) | Composite lithium cathode, preparation method thereof and lithium battery | |
| CN108270005B (en) | Lithium iron phosphate composite positive pole piece and preparation method thereof | |
| CN110858660B (en) | Lithium ion battery, preparation method thereof and electric vehicle | |
| CN114220947B (en) | Lithium metal battery negative electrode, current collector, preparation method of current collector and battery | |
| CN113835034A (en) | Method for measuring pre-lithium amount and pre-lithium capacity of pre-lithium battery | |
| CN116154100A (en) | Lithium supplementing positive electrode, preparation method thereof and lithium ion secondary battery | |
| CN111048749A (en) | Negative pole piece, lithium ion battery and manufacturing method thereof | |
| CN115295771A (en) | Positive electrode composite material, preparation method thereof, positive electrode plate and secondary battery | |
| CN115939309A (en) | Positive electrode containing lithium supplement composition, preparation method thereof and lithium ion battery | |
| JP2012009283A (en) | Lithium-ion secondary battery | |
| CN110993901A (en) | Low-internal-resistance quick-charging and quick-discharging lithium ion power battery | |
| CN113036082B (en) | Positive pole piece, preparation method of positive pole piece and lithium ion secondary battery | |
| CN117559013A (en) | Lithium supplementing agent composite material and preparation method and application thereof | |
| CN116914119A (en) | Lithium supplementing anode and preparation method and application thereof | |
| CN218867198U (en) | Battery and electric equipment | |
| CN109817467B (en) | Composite cathode material and preparation method thereof, and chemical power supply and preparation method thereof | |
| CN115084433B (en) | Positive pole piece and sodium ion battery | |
| CN217239505U (en) | Lithium ion battery positive pole piece and lithium ion battery |
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 |