Electrode lithium supplementing method and preparation method of lithium battery

Abstract

The invention discloses an electrode lithium supplementing method and a preparation method of a lithium battery, and the electrode lithium supplementing method comprises the following steps: S1, pre-lithiation of a negative plate: in an inert gas atmosphere, putting the negative plate into an electrolyte with the water content of less than 200ppm for charging, when the negative plate is charged, the current multiplying power is 0.1 C-3C, and the moisture content in the inert gas atmosphere is less than 500ppm, so that an SEI film is formed on the surface of the negative plate; and S2, performing film pressing on the negative plate: performing drying treatment on the negative plate, and performing film pressing and coating on the surface of the negative plate. The lithium supplement effect can be improved, the production cost is reduced, the pole piece transportation safety is improved, and the lithium battery performance is improved.

Description

[0001] This case is a divisional application based on the invention patent with application date of January 4, 2024, application number 202410013256X, and name "A method for replenishing lithium in electrodes and a method for preparing lithium batteries" as the parent case. Technical Field

[0002] The invention relates to the technical field of lithium ion battery production, in particular to a method for replenishing lithium in electrodes and a method for preparing a lithium battery. Background Art

[0003] Lithium-ion batteries are widely used in electric vehicles, digital electronic devices, aerospace vehicles and other fields due to their high energy density and long cycle life. During the first charging process of lithium-ion batteries, an SEI film, i.e. a solid electrolyte film with a thickness of 5-50nm, will form on the negative electrode surface. In the traditional production process of lithium-ion battery cells, the bare cells are usually wound or stacked, and then placed in a battery shell and injected with electrolyte for formation treatment. This will lead to an overall decrease in the concentration of lithium-ion batteries in the battery cells, which in turn causes a decrease in battery capacity, a decrease in the first efficiency, and a decrease in the potential for battery cycle life.

[0004] In this field, in order to solve the above problems, the method of replenishing lithium ions to the negative electrode is currently adopted to improve the problem of reduced initial efficiency of the battery and extend the cycle life of the battery. There are many existing lithium replenishment technologies, and the following two methods are commonly used: the first method is to first cover the lithium strip on the surface of the positive and negative electrode sheets with a roller to replenish lithium for the positive and negative electrodes, such as the Chinese patent document "A method for replenishing lithium for a pole sheet and a device for replenishing lithium for a pole sheet" with publication number CN113690400A. The second method is to charge the negative electrode for the first time before winding or stacking, complete pre-lithiation before assembling the bare battery cell, form an SEI film, and then complete the lithium replenishment.

[0005] The first method has a significant lithium supplementation effect and a simple production plan, but it involves the use of lithium metal in the production process. When lithium metal is supplemented in an air environment, it will react with moisture and oxygen in the air to generate lithium hydroxide and release heat during the production process. The existence form of lithium strips or lithium supplementation poles is formed after winding, which will cause the heat of the lithium strips or lithium supplementation poles to concentrate and cause local excessive temperatures, resulting in the lithium strips smoking and increasing the possibility of combustion, which reduces the safety of the production process. Although the second method can ensure the initial efficiency and cycle life of the battery, the active lithium exists in the SEI film that is finally formed, which cannot isolate the active lithium from the oxygen and moisture in the air, and thus easily affects the safety of transportation and storage during the production process. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide a method for replenishing lithium in an electrode and a method for preparing a lithium battery, which can improve the safety of transporting and storing electrodes while ensuring the lithium replenishment effect.

[0007] In order to solve the above technical problems, the technical solution adopted by the present invention is: The lithium replenishing method of the electrode comprises the following steps: S1: pre-lithiation of the negative electrode sheet: introducing an inert gas into the reaction chamber to form an inert gas atmosphere, placing the negative electrode sheet in an electrolyte with a water content of less than 200 ppm for charging, the current rate of the negative electrode sheet during charging is 0.1C-3C and the water content in the inert gas atmosphere is less than 500 ppm, so that a SEI film is formed on the surface of the negative electrode sheet; S2: Laminating the negative electrode sheet: After the negative electrode sheet is dried, the surface of the negative electrode sheet is laminated and coated.

[0008] In order to solve the above problem, another technical solution adopted by the present invention is: A method for preparing a lithium battery comprises the following steps: S1: preparing positive electrode slurry and negative electrode slurry respectively; S2: homogenizing the positive electrode slurry and the negative electrode slurry respectively, coating the homogenized positive electrode slurry and the negative electrode slurry on the surface of the positive current collector and the negative current collector respectively to form a positive electrode sheet and a negative electrode sheet, and then baking the positive electrode sheet and the negative electrode sheet and winding them for standby use to form a positive electrode sheet roll and a negative electrode sheet roll; S3: pre-lithiate the positive electrode sheet roll and the negative electrode sheet roll respectively by the electrode lithium replenishment method according to any one of claims 1 to 7, and flatten the electrode sheet rolls; S4: After die-cutting and powder-sweeping the pre-lithiated positive electrode sheets and negative electrode sheets in turn, they are stacked in an inert gas atmosphere to form bare cells, which are then packaged in turn to obtain lithium batteries.

[0009] The beneficial effects of the present invention are as follows: placing the negative electrode sheet in an electrolyte with a water content of less than 200ppm in an inert gas atmosphere for charging, isolating the electrode sheet from the air during the pre-lithiation process, and controlling the water content in the electrolyte and the inert gas atmosphere, reducing the probability of the electrode sheet reacting with water, thereby reducing the generation of lithium hydroxide, and controlling the charging rate at the same time, while ensuring the lithium replenishment effect while reducing the generation of irreversible lithium compounds in the electrode sheet. After the pre-lithiation of the negative electrode sheet is completed, the negative electrode sheet is coated to isolate the electrode sheet from the air, and at the same time, the surfaces of the negative electrode sheet do not contact each other, avoiding local overheating, so that the present invention can improve the safety of the electrode sheet during transportation and storage while ensuring the lithium replenishment effect. In addition, in the present invention, only the negative electrode sheet is pre-lithiation treated, and the active lithium inside the battery is not consumed, so that the lithium replenishment effect is further improved. DETAILED DESCRIPTION

[0010] In order to explain the technical content, achieved objectives and effects of the present invention in detail, the following is an explanation in conjunction with the implementation modes.

[0011] The lithium replenishing method of the electrode comprises the following steps: S1: Pre-lithiation of the negative electrode sheet: Inert gas is introduced into the reaction chamber to form an inert gas atmosphere, and the negative electrode sheet is placed in an electrolyte with a water content of less than 200 ppm for charging. The current rate of the negative electrode sheet during charging is 0.1C~3C and the water content in the inert gas atmosphere is less than 500 ppm, so that a SEI film is formed on the surface of the negative electrode sheet; S2: Laminating the negative electrode sheet: After the negative electrode sheet is dried, the surface of the negative electrode sheet is laminated and coated.

[0012] From the above description, it can be seen that the beneficial effects of the present invention are: placing the negative electrode sheet in an electrolyte with a water content of less than 200ppm in an inert gas atmosphere for charging, so that the electrode sheet is isolated from the air during the pre-lithiation process, directly charging the negative electrode sheet, improving the lithium replenishment effect, and controlling the water content in the electrolyte and the inert gas atmosphere, reducing the probability of the electrode sheet reacting with moisture and oxygen, thereby reducing the generation of lithium hydroxide and lithium oxide, and controlling the charging rate at the same time, while ensuring the lithium replenishment effect while reducing the generation of irreversible lithium compounds in the electrode sheet. After the pre-lithiation of the negative electrode sheet is completed, the negative electrode sheet is coated so that the electrode sheet is isolated from the air, and at the same time, the surface of the negative electrode sheet does not contact each other, avoiding local overheating, so that the present invention can ensure the lithium replenishment effect while improving the safety of the electrode sheet during transportation. In addition, in the present invention, only the negative electrode sheet is pre-lithiation treated, and the active lithium inside the battery is not consumed, so that the lithium replenishment effect is further improved. Furthermore, the specific step of lamination is to respectively coat the two sides of the negative electrode sheet in the thickness direction with the lamination film and to bond the lamination films on the two sides of the negative electrode sheet in the thickness direction so that the lamination films extend beyond the negative electrode sheet.

[0013] From the above description, it can be seen that by coating the negative electrode sheet in this way, the negative electrode sheet is completely wrapped and thus completely isolated from the air. At the same time, the surfaces of the negative electrode sheet are prevented from contacting each other, which facilitates the winding of the negative electrode sheet and avoids local overheating.

[0014] Furthermore, the base material of the press-coated film is PP, PE, PVC or PVDC, and at least one of the following materials is coated on the surface of the main material: alumina ceramic particles, anti-perovskite (LLZO) solid electrolyte, garnet (LLTO) solid electrolyte or sodium superion (NASICON) solid electrolyte. Optionally, the thickness of the press-coated film is 8μm~32μm, preferably 14~20μm. Preferably, the base material of the press-coated film is PP, PE, PVC or PVDC, wherein PP is a high polymer polypropylene, PE is polyethylene, PVC is polyvinyl chloride, and PVDC is polyvinylidene chloride. PP and PE are used as diaphragm base films for lithium-ion batteries due to their excellent HF corrosion resistance, good high temperature stability and anti-dissolution performance. In order to improve the anti-puncture performance of the laminated film, metal oxide ceramic particles can also be coated on the surface of the laminated film. Commonly used metal oxide ceramic particles are aluminum oxide and oxide solid electrolytes, and the use of other types of ceramic particles is not excluded. The above materials have good insulation properties and hardness, good compatibility with lithium ions and facilitate the passage of lithium ions.

[0015] Furthermore, the thickness of the laminated film is 8-32 μm, and preferably, the thickness of the laminated film is 14-20 μm.

[0016] Further, the components of the electrolyte include at least two of lithium hexafluorophosphate, lithium difluorophosphate, lithium tetrafluoroborate, lithium bis(oxalatoborate), lithium difluorooxalatoborate, lithium bis(trifluoromethylsulfonamide)imide, lithium bis(fluorosulfonyl)imide, tris(pentafluorophenyl)borane, tris(pentafluoroborane)phosphine, tris(pentafluorophenyl)silane, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, ethyl butyrate, methylpropyl carbonate, halogenated ethylene carbonate, propylene carbonate, methylpropyl carbonate, γ-butyrolactone and γ-valerolactone.

[0017] Furthermore, the current rate of the negative electrode sheet during charging is 0.1C~1C.

[0018] From the above description, it can be seen that when the current rate of the negative electrode sheet is higher, the more irreversible lithium compounds are produced by the negative electrode sheet, the more serious the dead lithium phenomenon is, and the lithium replenishment effect of the negative electrode sheet is affected. When the current rate of the negative electrode sheet is too low, the negative electrode sheet cannot be fully pre-lithiated, which will also affect the physical and chemical effects of the negative electrode sheet. Therefore, when the negative electrode sheet is charged within this current rate range, it not only ensures the pre-lithiation process, but also ensures the amount of lithium replenishment, which can achieve the best pre-lithiation effect.

[0019] Furthermore, the temperature of the electrolyte is 15°C to 35°C.

[0020] From the above description, it can be seen that under high temperature environment, the decomposition of the electrolyte will be accelerated, making the ions inside the electrolyte uncontrollable. And at high temperature, the electrolyte reacts with the materials in the negative electrode plate, causing it to gradually degrade, which will not only reduce the energy density and charge and discharge efficiency of the negative electrode plate, but also may cause safety problems, increasing the potential risk of the structure of the negative electrode plate being destroyed and unable to be used. And under high temperature environment, the volatilization rate of the electrolyte increases, and the difference between the concentration of the internal components of the electrolyte and the initial component concentration gradually increases with time, resulting in inconsistent lithium replenishment of the negative electrode plate, and then uneven battery performance. Lithium replenishment in a low temperature environment may cause the viscosity of the electrolyte to increase, the migration rate of lithium ions in the electrolyte to decrease, resulting in poor charging efficiency of the negative electrode plate, and a decrease in lithium replenishment efficiency, making the quality of the lithium replenishment negative electrode plate uncontrollable. Therefore, during the lithium replenishment process, the electrolyte should be kept at a suitable temperature as much as possible to ensure the uniformity and stability of the SEI film of the negative electrode plate. The optimal electrolyte temperature is 25°C.

[0021] A method for preparing a lithium battery comprises the following steps: S1: preparing positive electrode slurry and negative electrode slurry respectively; S2: homogenizing the positive electrode slurry and the negative electrode slurry respectively, coating the homogenized positive electrode slurry and the negative electrode slurry on the surface of the positive current collector and the negative current collector respectively to form a positive electrode sheet and a negative electrode sheet, and then baking the positive electrode sheet and the negative electrode sheet and winding them for standby use to form a positive electrode sheet roll and a negative electrode sheet roll; S3: pre-lithiate the positive electrode sheet roll and the negative electrode sheet roll respectively by the above-mentioned electrode lithium replenishment method, and flatten the electrode sheet roll; S4: After die-cutting and powder-sweeping the pre-lithiated positive electrode sheets and negative electrode sheets in turn, they are stacked in an inert gas atmosphere to form bare cells, which are then packaged in turn to obtain lithium batteries.

[0022] Furthermore, the positive electrode sheet is made of a positive electrode current collector, a positive electrode active material, a binder and a conductive agent. The positive electrode current collector is at least one of copper foil, tin foil, aluminum foil, titanium foil and nickel foil; the positive electrode active material is at least one of lithium nitride, lithium iron phosphate, lithium titanate, lithium cobaltate, ternary lithium compound, lithium nickelate and lithium manganate; the binder is at least one of polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene rubber, polyacrylate, ethylene carbonate and methyl carbonate; the conductive agent is at least one of natural graphite, artificial graphite, carbon fiber, carbon nanotube, hard carbon, soft carbon and carbon black.

[0023] Further, the positive electrode slurry includes polyvinylidene fluoride, Super-P, carbon nanotube-sulfur and LFP, and the ratio of polyvinylidene fluoride, Super-P, carbon nanotube-sulfur and LFP is 1.73-1.83: 1.31-1.43: 29.03-31.25: 65.71-67.711.

[0024] Furthermore, the negative electrode sheet is made of a negative electrode current collector, a negative electrode active material, a binder and a conductive agent, and the negative electrode current collector is composed of one or more of copper foil, silver foil, tin foil, aluminum foil, gold foil and titanium foil; The negative electrode active material is composed of one or more of natural graphite, artificial graphite, carbon nanotubes, hard carbon, soft carbon, and nitrides, sulfides, and phosphides of elements such as lithium, silicon, tin, aluminum, sodium, and manganese. Preferably, the negative electrode active material is artificial graphite, carbon nanotubes, and hard carbon, and the addition ranges are 45-75%, 0.01-1.5%, and 15-50%, respectively. The binder is composed of one or more of polyvinylidene fluoride, polytetrafluoroethylene, styrene-butadiene rubber, polyacrylate, ethylene carbonate, and methyl carbonate. The conductive agent is composed of one or more of graphite, petroleum coke, needle coke, carbon fiber, hard carbon, soft carbon, carbon black, and sodium carboxymethyl cellulose. The synthesis of the negative electrode slurry requires the use of a solvent, which can be selected from one or more of N-methylpyrrolidone (NMP), dimethylformamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO), deionized water, methanol, propanol, and acetone.

[0025] Further, the negative electrode slurry includes carboxymethyl cellulose, Super-P, graphite, hard carbon and styrene-butadiene rubber, and the ratio of carboxymethyl cellulose, Super-P, graphite, hard carbon and styrene-butadiene rubber is 1.16-1.24: 2.23-2.33: 41.98-42.16: 17.96-18.06: 1.3-1.38: 34.91-35.37.

[0026] The specific implementation of the present invention is: A method for preparing a lithium battery comprises the following steps: S1: Prepare positive electrode slurry and negative electrode slurry respectively. The positive electrode slurry includes N-methyl-2-pyrrolidone, polyvinylidene fluoride, Super-P, carbon nanotube-sulfur and LFP, and the ratio of each component is 26.5:1.3:1:22.3:48.7; the negative electrode slurry includes deionized water, carboxymethyl cellulose, Super-P, graphite, hard carbon, N-methyl-2-pyrrolidone and styrene-butadiene rubber, and the ratio of each component is 49.1:0.9:1.7:31.3:13.4:1:26.1.

[0027] S2: The positive electrode slurry and the negative electrode slurry are homogenized respectively, and the homogenized positive electrode slurry and negative electrode slurry are coated on the surface of the positive current collector and the negative current collector respectively to form positive electrode sheets and negative electrode sheets, wherein the online speed of the positive electrode coating is 0.05m / min~3m / min, and the online speed of the negative electrode coating is 0.05m / min~3m / min, and the positive electrode sheets and the negative electrode sheets are baked and then wound up for standby use to form positive electrode sheet rolls and negative electrode sheet rolls, wherein the thickness of the positive electrode is 116~122μm, preferably 119μm, and the thickness of the negative electrode is 88~94μm, preferably 91μm; preferably, the positive electrode collector is aluminum foil, and the material of the negative electrode collector is copper foil.

[0028] S3: The positive electrode sheet roll and the negative electrode sheet roll are pre-lithiated by an electrode lithium replenishment method, specifically, in an inert gas atmosphere, the negative electrode sheet is placed in an electrolyte with a water content of less than 200ppm for charging, the current rate of the negative electrode sheet during charging is 0.1C~3C and the water content in the inert gas atmosphere is less than 500ppm, so that a SEI film is formed on the surface of the negative electrode sheet; in the pre-lithiation step of the positive electrode sheet roll and the negative electrode sheet roll, one end of the positive electrode sheet roll and the negative electrode sheet roll are both sent to the lithium replenishment device, and the lithium replenishment device The pressure roller rolls the electrode flat and performs pre-lithiation. After that, the negative electrode is dried and then the surface of the negative electrode is coated with a film. During the pre-lithiation of the electrode, inert gas is continuously introduced to control the air pressure inside the reaction chamber of the lithium replenishing device to be slightly higher than the external air pressure. The air pressure inside the reaction chamber of the lithium replenishing device is 18-37Pa, so that the electrolyte in the reaction chamber maintains a low moisture content and high atmosphere purity, and thus does not produce hydrofluoric acid to affect the pre-lithiation process of the electrode, avoiding contact with oxygen during the pre-lithiation process of the electrode, and ensuring the structural stability of the SEI film.

[0029] S4: After die-cutting and powder sweeping the pre-lithiation positive and negative electrodes in turn, the sheets are stacked in an inert gas atmosphere to form a bare cell, and a lithium battery is obtained after packaging. Specifically, the packaging process includes the following steps in sequence: spot welding, shell punching, packaging, baking at a temperature of 85±10°C, liquid injection and standing, primary degassing, polymerization reaction (curing temperature is 50-80°C, curing time is 12-36h), formation (charge termination voltage 3.65V, discharge termination voltage 2.5V), aging (24±2h), secondary degassing (vacuum degree is -85kPa), secondary sealing, capacity division, and finally a polymer lithium-ion battery is made. The above packaging processes are all existing technologies for lithium battery production and will not be repeated here. Among them, the purpose of baking is to remove the moisture content inside the bare cell and the aluminum-plastic film to avoid the reaction of fluoride and water to form hydrofluoric acid after the electrolyte is injected. Liquid injection is to inject electrolyte into bare cells with a moisture content of less than 200ppm, soak the bare cells, and let them stand for 12-24 hours to ensure that the bare cells are thoroughly soaked; the purpose of primary degassing is to remove the gas generated during the polymerization reaction and excess electrolyte for subsequent processing; formation is to charge and discharge the lithium-ion battery to further improve the stability of the SEI film structure; the role of capacity separation is to perform charge and discharge tests on the battery, determine the electrical performance of each battery, and classify them; aging is to let it stand at room temperature for 12-24 hours, which can make the SEI film formed by formation more stable; the purpose of secondary degassing is to remove the gas generated during the formation process.

[0030] The specific parameters of the first to sixth embodiments of the present invention are shown in Table 1.

[0031] Table 1

[0032] Table 2

[0033] According to the data in Table 1 and Table 2, the initial efficiency increases with the increase of the battery rate, but the capacity retention rate after 50 cycles and 500 cycles also decreases; and according to Example 4 to Example 6, as the online speed of the electrode increases, the initial efficiency decreases, and the capacity retention rate after 50 cycles and 500 cycles also decreases.

[0034] The first efficiency is the percentage of the divided capacity to the formed capacity. The capacity retention rates in Tables 1 and 2 are obtained according to the GB / T 36276-2018 standard test.

[0035] In summary, the present invention provides an electrode lithium replenishment method and a lithium battery preparation method, which does not require the use of metallic lithium for lithium replenishment during the production process, thereby reducing the cost of lithium replenishment. After the negative electrode is pre-lithiated, the electrode is prevented from contacting with air and moisture, thereby improving the transportation safety of the electrode.

[0036] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent transformations made using the contents of the present invention specification, or directly or indirectly applied in related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A lithium supplementation method for an electrode, characterized in that: The following steps are involved: S1: pre-lithiation of the negative electrode sheet: introducing an inert gas into the reaction chamber to form an inert gas atmosphere, placing the negative electrode sheet in an electrolyte with a water content of less than 200 ppm for charging, the current rate of the negative electrode sheet during charging is 0.1C-3C and the water content in the inert gas atmosphere is less than 500 ppm, so that a SEI film is formed on the surface of the negative electrode sheet; S2: laminating the negative electrode sheet: after drying the negative electrode sheet, laminating films are respectively applied on both sides of the negative electrode sheet in the thickness direction; The material of the substrate of the press-coated film is PP, PE, PVC or PVDC, and metal oxide ceramic particles are coated on the surface of the substrate of the press-coated film.

2. The method for replenishing lithium in an electrode according to claim 1, characterized in that: The thickness of the laminated film is 8-32 μm.

3. The lithium replenishing method for an electrode according to claim 1, characterized in that: The components of the electrolyte include at least two of lithium hexafluorophosphate, lithium difluorophosphate, lithium tetrafluoroborate, lithium bis(oxalatoborate), lithium difluorooxalatoborate, lithium bis(trifluoromethylsulfonamide)imide, lithium bis(fluorosulfonyl)imide, tris(pentafluorophenyl)borane, tris(pentafluoroborane)phosphorus, tris(pentafluorophenyl)silane, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, ethyl butyrate, methylpropyl carbonate, halogenated ethylene carbonate, propylene carbonate, methylpropyl carbonate, γ-butyrolactone and γ-valerolactone.

4. The lithium replenishing method for an electrode according to claim 1, characterized in that: The current rate of the negative electrode sheet during charging is 0.1C~1C.

5. A method for preparing a lithium battery, characterized in that: The following steps are involved: S1: preparing positive electrode slurry and negative electrode slurry respectively; S2: homogenizing the positive electrode slurry and the negative electrode slurry respectively, coating the homogenized positive electrode slurry and the negative electrode slurry on the surface of the positive current collector and the negative current collector respectively to form a positive electrode sheet and a negative electrode sheet, and then baking the positive electrode sheet and the negative electrode sheet and winding them for standby use to form a positive electrode sheet roll and a negative electrode sheet roll; S3: pre-lithiate the positive electrode sheet roll and the negative electrode sheet roll respectively by the electrode lithium replenishment method according to any one of claims 1 to 6, and flatten the electrode sheet rolls; S4: After die-cutting and powder-sweeping the pre-lithiated positive electrode sheets and negative electrode sheets in turn, they are stacked in an inert gas atmosphere to form bare cells, which are then packaged in turn to obtain lithium batteries.

6. The method for preparing a lithium battery according to claim 5, characterized in that: The positive electrode slurry comprises polyvinylidene fluoride, Super-P, carbon nanotube-sulfur and LFP, and the ratio of polyvinylidene fluoride, Super-P, carbon nanotube-sulfur and LFP is 1.73-1.83: 1.31-1.43: 29.03-31.25: 65.71-67.

71.

7. The method for preparing a lithium battery according to claim 5, characterized in that: The negative electrode slurry includes carboxymethyl cellulose, Super-P, graphite, hard carbon and styrene-butadiene rubber, and the ratio of carboxymethyl cellulose, Super-P, graphite, hard carbon and styrene-butadiene rubber is 1.16-1.24: 2.23-2.33: 41.98-42.16: 17.96-18.06: 1.3-1.38: 34.91-35.37.

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