NH2 - Quasi-solid hybrid lithium-ion battery and method for preparing a separator

Abstract

This invention discloses NH2 ‑ A method for preparing a hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery and its separator was first proposed. An anionic MOZ-201-NH2 crystal material was synthesized via a hydrothermal method. Then, it was blended with lithium bis(trifluoromethanesulfonyl)imide and polyethylene oxide to obtain NH2. ‑ A hydrogen-bonded crosslinked solid polymer viscous liquid, when poured onto a polytetrafluoroethylene (PTFE) template and allowed to stand, yields NH2. ‑ Hydrogen-bonded cross-linked polymer solid membranes were used, and finally assembled into batteries, resulting in NH2 with good thermal stability and high lithium-ion transference number. ‑ A hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery. At room temperature, this material exhibits a theoretical specific capacity of 170 mAh / g at a rated capacitance of 1C. After 50 cycles at a rated capacitance of 1C, the discharge specific capacity is 124 mAh / g, and its coulombic efficiency remains around 100%.

Description

Technical Field

[0001] This invention belongs to the field of organometallic zeolite and solid-state battery technology, specifically relating to NH2. - The preparation method of hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery separator also involves NH2. - A method for preparing hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion batteries. Background Technology

[0002] With the rapid development of technology, people have begun to use gasoline-powered vehicles, which have brought convenience to travel. However, the large-scale use of gasoline-powered vehicles has led to the excessive consumption of fossil fuels and caused serious environmental pollution problems. Faced with the gradual depletion of global fossil fuels, people have begun to use new energy vehicles to replace gasoline-powered vehicles. With the large-scale use of new energy vehicles, secondary batteries play an extremely important role in their lifespan. Lithium-ion batteries are very popular among researchers because of their high energy density, which is 6 to 7 times that of currently commercially available lead-acid batteries, and their stable cycle performance. Lithium-ion batteries can be divided into two main categories: lithium-ion batteries and solid-state lithium batteries. Lithium-ion batteries use liquid electrolytes, which are prone to leakage and fire, posing safety hazards. Therefore, research on solid-state lithium metal batteries has received widespread attention.

[0003] Solid-state lithium metal batteries (SLMs) are characterized by high energy density, no leakage, and good cycle stability. In recent years, researchers have focused on the research progress of solid electrolyte membranes within SLM batteries. Although assembled SLM batteries have exhibited excellent capacity and high cycle stability, the lithium-ion transference number remains low. A low lithium-ion transference number first reduces the effective ionic conductivity and secondly causes severe concentration polarization of the electrolyte during charge and discharge, resulting in uneven lithium-ion deposition and affecting the battery's rate performance. Therefore, efforts should be made to increase the lithium-ion transference number of the polymer electrolyte as much as possible. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing a cross-linked quasi-solid-state hybrid lithium-ion battery separator, which solves the problem of low lithium-ion transference number in existing quasi-solid-state lithium metal battery separators, resulting in poor battery cycle rate.

[0005] The purpose of this invention is to provide an NH2 - A method for preparing hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion batteries.

[0006] The first technical solution adopted in this invention is NH2 - The preparation method of hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery separator, with specific operation steps as follows:

[0007] Step 1: Zinc salt, pentamethyltetrazole, and 5-aminoisophthalic acid are mixed in N,N-dimethylformamide. After adding 4-methylammonium hydroxide, the mixture is reacted at high temperature. After naturally cooling to room temperature, it is washed, filtered, and dried to obtain yellowish-brown crystals A.

[0008] Step 2: Place the yellowish-brown crystal A into a mortar and grind it to obtain yellowish-brown powder B;

[0009] Step 3: Weigh out yellowish-brown powder B, lithium bis(trifluoromethanesulfonyl)imide and polyethylene oxide, add N,N-dimethylformamide solution, and stir at room temperature to obtain yellowish-brown viscous liquid C;

[0010] Step 4: Place the yellowish-brown viscous liquid C in a vacuum drying oven at 60°C for 10 minutes to eliminate internal air bubbles. Then pour it into a polytetrafluoroethylene mold and dry it in an oven for 12 hours to obtain a yellowish-brown polymer solid film D.

[0011] Step 5: Cut the dried polymer film D into small round pieces to obtain polymer solid membrane sheet E, and place it in a glove box with a water oxygen value of less than 0.01 ppm.

[0012] The invention is further characterized in that,

[0013] In step 1, the zinc salt can be replaced by either zinc chloride or zinc nitrate hexahydrate; the molar ratio of the zinc salt, pentamethyltetrazole, and 5-aminoisophthalic acid is 1:1:1; the oven temperature is set at 100–160°C, the reaction time is between 24 and 60 hours, the drying temperature is between 50 and 80°C, and the drying time is between 10 and 18 hours.

[0014] In step 1, the yellowish-brown crystal A is a MOZ-201-NH2 anionic metal-organic zeolite framework material.

[0015] In step 3, the mass ratio of yellowish-brown powder B, lithium bis(trifluoromethanesulfonyl)imide, and polyethylene oxide is 1:1:8, and the mixture is stirred at room temperature for no less than 48 hours.

[0016] In step 4, the dimensions of the polytetrafluoroethylene mold are 10*10*0.5 cm.

[0017] The diameter of the cut piece in step 5 is 19mm.

[0018] The second technical solution adopted in this invention is NH2 - The preparation method of hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery, with specific operation steps as follows:

[0019] Step 1: Weigh lithium iron phosphate, carbon black, and polyvinylidene fluoride (PVDF), place them in an agate mortar, and grind them thoroughly. Add N,N-2-methylpyrrolidone, transfer the mixture to a small bottle, and stir thoroughly with a magnetic stir bar to form a uniform and viscous black slurry F. Coat the prepared black slurry F onto aluminum foil using a scraper, vacuum dry it at 60°C for 24 hours, and cut it into thin slices to obtain lithium iron phosphate electrode sheets G.

[0020] Step 2: The prepared lithium iron phosphate electrode G, the polymer solid membrane E dipped in electrolyte, and the lithium negative electrode are assembled into a CR2032 battery. The entire assembly process is carried out in a glove box with a water oxygen value of less than 0.01 ppm for subsequent performance testing.

[0021] In step 1, the mass ratio of lithium iron phosphate, carbon black, and polyvinylidene fluoride (PVDF) is 7:2:1, and the mixture is stirred at room temperature for at least 24 hours, using a scraper with a thickness of 100 micrometers. In step 2, the lithium iron phosphate electrode G can be made from LiNi... 0.8 Mn 0.1 Co 0.1 O2 is used instead.

[0022] The diameter of the sheet mentioned in step 1 is 12 mm.

[0023] The electrolyte in step 2 is a mixture of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium nitrate, wherein the molar ratio of LiTFSI to lithium nitrate is 1:5.

[0024] The synthesis principle of key steps in this invention:

[0025] (I) Synthesis of precursor: First, a highly ordered crystalline structure of MOZ-201-NH2 anionic metal-organic zeolite framework material was synthesized. This metal-organic zeolite framework has a special nanotube structure, which can facilitate the transfer of lithium ions in subsequent experiments.

[0026] (ii) NH2 - Preparation of hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery separator material: We chose to blend the precursor MOZ-201-NH2 with polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and uniformly disperse MOZ-201-NH2 in a polyethylene oxide (PEO) matrix to prepare a polymer solid-state separator. This effective combination method does not change the crystal structure of the precursor, but instead promotes chain segment movement and interfacial contact, promoting lithium-ion migration, thereby improving the ionic conductivity of the polymer matrix.

[0027] (III) NH2 -The unique characteristics of hydrogen-bonded cross-linked quasi-solid-state hybrid lithium-ion battery separator materials: In the blending step adopted in this invention, N,N-dimethylformamide (DMF) is added. Due to the formation of cross-linked hydrogen bonds between the amino groups of the MOZ-201-NH2 anionic metal-organic zeolite framework material and the (C=O) groups of the amide molecules, the number of amide molecules coordinated with lithium ions is reduced. The coordination effect between lithium ions and C=O is weakened, which can promote the dissociation of the solvation structure of lithium ions and increase the migration number of lithium ions.

[0028] (iv) Utilizing NH2 - Hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery separator material for battery assembly: Traditional commercial lithium-ion batteries use liquid electrolytes, resulting in poor thermal stability and potential safety hazards. We chose to blend the precursor MOZ-201-NH2 with polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The resulting polymer solid-state separator effectively solves this problem, preventing lithium dendrites from forming and puncturing the separator during battery cycling, thus enhancing the battery's electrochemical and thermal stability.

[0029] The beneficial effects of this invention are:

[0030] (1) The precursor MOZ-201-NH2 metal-organic framework was synthesized by hydrothermal method. Applying MOF materials to the interface of covalently linked MOF-polymer hybrid electrolyte can provide a fast channel for ion transport, thereby improving ionic conductivity.

[0031] (2) NH2 was prepared by mold method and film scraping method. - Hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery separator materials and the required positive electrode sheets can effectively control the thickness of the separator and positive electrode sheets, thereby improving the battery's capacity and stability during cycling. This method can be used for any quasi-solid-state polymer lithium / sodium / potassium battery.

[0032] (3) Blending the precursor MOZ-201-NH2 with polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonylimide) (LiTFSI) to prepare polymer solid membrane sheets to replace traditional commercial membranes is an excellent, inexpensive and recyclable preparation method.

[0033] (4) This invention provides an NH2 - A method for preparing hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery separator material. This method can be used in any quasi-solid-state polymer lithium / sodium / potassium and other alkaline metal batteries, greatly improving the application range of the material.

[0034] (5) The special polymer used in this invention is polyethylene oxide (PEO). As the temperature increases, the viscosity of this polymer is better, which can make the polymer electrolyte interface contact the positive and negative electrodes better, thereby greatly improving the charge and discharge specific capacity and coulombic efficiency of the battery. Attached Figure Description

[0035] Figure 1 This invention is NH2 - Schematic diagram of the preparation process of hydrogen-bonded cross-linked quasi-solid-state hybrid lithium-ion battery separator material;

[0036] Figure 2 The X-ray diffraction patterns of the precursor MOZ-201-NH2 crystal material and the standard anionic metal-organic zeolite framework material are shown.

[0037] Figure 3 The NH2 prepared in this invention - The relationship between current and voltage in a hydrogen-bonded cross-linked quasi-solid-state hybrid lithium-ion battery at a scan rate of 0.01 mV / s;

[0038] Figure 4 The NH2 prepared in this invention - Electrochemical impedance spectroscopy of a hydrogen-bonded cross-linked quasi-solid-state hybrid lithium-ion battery;

[0039] Figure 5 The NH2 prepared in this invention - Current-time curves of hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion batteries and AC impedance spectra of the batteries before and after polarization, as shown in the illustration.

[0040] Figure 6 The NH2 prepared in this invention - The graph shows the relationship between efficiency and specific capacity of hydrogen-bonded cross-linked quasi-solid-state hybrid lithium-ion battery separator material after 50 cycles at a rated capacitance of 1C. Detailed Implementation

[0041] The NH2 provided by this invention - A method for preparing hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery separator material includes the synthesis of MOZ-201-NH2 crystal material, blending it with polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to prepare a solid polymer film, and assembling it with a lithium iron phosphate cathode and a lithium anode to form a quasi-solid-state polymer lithium battery.

[0042] The present invention will be further described below with reference to specific embodiments.

[0043] Example 1

[0044] Step 1: Zinc chloride (0.5 mmol, 0.068 g), pentamethyltetrazole (0.5 mmol, 0.042 g), and 5-aminoisophthalic acid (0.5 mmol, 0.083 g) were mixed in 5 ml of N,N-dimethylformamide (DMF), and two drops of 4-methylammonium hydroxide were added. The mixture was reacted at 120 °C for 40 hours, then allowed to cool naturally to room temperature. The mixture was then washed with N,N-dimethylformamide, filtered, and placed in a 50 °C forced-air drying oven. After drying for 18 hours, yellowish-brown crystals A were obtained.

[0045] Step 2: Place the yellowish-brown crystal A into a mortar and grind it to obtain yellowish-brown powder B.

[0046] Step 3: Weigh 0.125g of yellowish-brown powder B, 0.125g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 1g of polyethylene oxide (PEO) in a mass ratio of 1:1:8, add 20ml of N,N-dimethylformamide (DMF) solution, and stir at room temperature for 48 hours to obtain yellowish-brown viscous liquid C.

[0047] Step 4: Place the uniformly mixed yellowish-brown viscous liquid C in a vacuum drying oven at 60°C for 10 minutes to eliminate the formation of air bubbles inside the solvent. Then pour it into a polytetrafluoroethylene mold with dimensions of 10*10*0.5 cm and place it at room temperature for 12 hours to obtain a yellowish-brown polymer flexible diaphragm D.

[0048] Step 5: Cut the dried polymer film D into small circular pieces with a diameter of 19 mm to obtain polymer solid diaphragm sheet E, and place it in a glove box with a water oxygen value of less than 0.01 ppm.

[0049] Step 6: Weigh 0.35g of lithium iron phosphate, 1g of carbon black, and 0.05g of polyvinylidene fluoride (PVDF) in a mass ratio of 7:2:1. Place them in an agate mortar and grind them thoroughly. Add an appropriate amount of N,N-2-methylpyrrolidone (NMP), transfer to a small bottle, and stir thoroughly with a magnetic stirrer for 24 hours to form a uniform, viscous black slurry F. Coat the prepared black slurry F onto aluminum foil using a 100-micron thick film scraper, vacuum dry at 60℃ for 24 hours, and cut into thin slices with a diameter of 12mm to obtain the lithium iron phosphate electrode G.

[0050] Step 7: Assemble the prepared lithium iron phosphate electrode G, polymer solid separator E, and lithium negative electrode into a CR2032 battery for subsequent performance testing. The battery is assembled in the following order: positive electrode shell, lithium iron phosphate electrode G, polymer solid separator E dipped in electrolyte, lithium sheet, gasket, spring sheet, and negative electrode shell. The entire process is carried out in a glove box with an oxygen content of less than 0.01 ppm.

[0051] Example 2

[0052] Step 1: Zinc nitrate hexahydrate (0.5 mmol, 0.148 g), pentamethyltetrazole (0.5 mmol, 0.042 g), and 5-aminoisophthalic acid (0.5 mmol, 0.083 g) were mixed in 5 ml of N,N-dimethylformamide (DMF), and two drops of 4-methylammonium hydroxide were added. The mixture was reacted at 150 °C for 32 hours, then allowed to cool naturally to room temperature. The mixture was then washed with N,N-dimethylformamide, filtered, and placed in an 80 °C drying oven. After drying for 12 hours, yellowish-brown crystals A were obtained.

[0053] Step 2: Place the yellowish-brown crystal A into a mortar and grind it to obtain yellowish-brown powder B.

[0054] Step 3: Weigh 0.125g of yellowish-brown powder B, 0.125g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 1g of polyethylene oxide (PEO) in a mass ratio of 1:1:8, add 20ml of N,N-dimethylformamide (DMF) solution, and stir at room temperature for 80 hours to obtain yellowish-brown viscous liquid C.

[0055] Step 4: Place the uniformly mixed yellowish-brown viscous liquid C in a vacuum drying oven at 60°C for 10 minutes to eliminate the formation of air bubbles inside the solvent. Then pour it into a polytetrafluoroethylene mold with dimensions of 10*10*0.5 cm and place it at room temperature for 12 hours to obtain a yellowish-brown polymer flexible diaphragm D.

[0056] Step 5: Cut the dried polymer film D into small circular pieces with a diameter of 19 mm to obtain polymer solid diaphragm sheet E, and place it in a glove box with a water oxygen value of less than 0.01 ppm.

[0057] Step 6: Weigh 0.35g of lithium iron phosphate, 1g of carbon black, and 0.05g of polyvinylidene fluoride (PVDF) in a mass ratio of 7:2:1. Place them in an agate mortar and grind them thoroughly. Add an appropriate amount of N,N-2-methylpyrrolidone (NMP), transfer to a small bottle, and stir thoroughly with a magnetic stirrer for 32 hours to form a uniform, viscous black slurry F. Coat the prepared black slurry F onto aluminum foil using a 100-micron thick film scraper, vacuum dry at 60℃ for 24 hours, and cut into thin slices with a diameter of 12mm to obtain lithium iron phosphate electrode sheets G.

[0058] Step 7: Assemble the prepared lithium iron phosphate electrode G, polymer solid-state separator E, and lithium negative electrode into a CR2032 battery for subsequent performance testing. The battery is assembled in the following order: positive electrode shell, lithium manganese oxide electrode G, polymer solid-state separator E dipped in electrolyte, lithium sheet, gasket, spring sheet, and negative electrode shell. The entire process is carried out in a glove box with a water oxygen value of less than 0.01 ppm.

[0059] Example 3

[0060] Step 1: Zinc acetate (0.5 mmol, 0.092 g), pentamethyltetrazole (0.5 mmol, 0.042 g), and 5-aminoisophthalic acid (0.5 mmol, 0.083 g) were mixed in 5 ml of N,N-dimethylformamide (DMF), and two drops of 4-methylammonium hydroxide were added. The mixture was reacted at 100 °C for 48 hours, then allowed to cool naturally to room temperature. The mixture was then washed with N,N-dimethylformamide, filtered, and placed in a 50 °C forced-air drying oven. After drying for 18 hours, yellowish-brown crystals A were obtained.

[0061] Step 2: Place the yellowish-brown crystal A into a mortar and grind it to obtain yellowish-brown powder B.

[0062] Step 3: Weigh 0.125g of yellowish-brown powder B, 0.125g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 1g of polyethylene oxide (PEO) in a mass ratio of 1:1:8, add 20ml of N,N-dimethylformamide (DMF) solution, and stir at room temperature for 48 hours to obtain yellowish-brown viscous liquid C.

[0063] Step 4: Place the uniformly mixed yellowish-brown viscous liquid C in a vacuum drying oven at 60°C for 10 minutes to eliminate the formation of air bubbles inside the solvent. Then pour it into a polytetrafluoroethylene mold with dimensions of 10*10*0.5 cm and place it at room temperature for 12 hours to obtain a yellowish-brown polymer flexible diaphragm D.

[0064] Step 5: Cut the dried polymer film D into small circular pieces with a diameter of 19 mm to obtain polymer solid diaphragm sheet E, and place it in a glove box with a water oxygen value of less than 0.01 ppm.

[0065] Step 6: Weigh 0.35g of lithium iron phosphate, 1g of carbon black, and 0.05g of polyvinylidene fluoride (PVDF) in a mass ratio of 7:2:1. Place them in an agate mortar and grind them thoroughly. Add an appropriate amount of N,N-2-methylpyrrolidone (NMP), transfer to a small bottle, and stir thoroughly with a magnetic stirrer for 24 hours to form a uniform, viscous black slurry F. Coat the prepared black slurry F onto aluminum foil using a 100-micron thick film scraper, vacuum dry at 60℃ for 24 hours, and cut into thin slices with a diameter of 12mm to obtain the lithium iron phosphate electrode G.

[0066] Step 7: Assemble the prepared lithium iron phosphate electrode G, polymer solid separator E, and lithium negative electrode into a CR2032 battery for subsequent performance testing. The battery is assembled in the following order: positive electrode shell, lithium iron phosphate electrode G, polymer solid separator E dipped in electrolyte, lithium sheet, gasket, spring sheet, and negative electrode shell. The entire process is carried out in a glove box with an oxygen content of less than 0.01 ppm.

[0067] Example 4

[0068] Step 1: Zinc nitrate hexahydrate (0.5 mmol, 0.148 g), pentamethyltetrazole (0.5 mmol, 0.042 g), and 5-aminoisophthalic acid (0.5 mmol, 0.083 g) were mixed in 5 ml of N,N-dimethylformamide (DMF), and two drops of 4-methylammonium hydroxide were added. The mixture was reacted at 160 °C for 28 hours, then allowed to cool naturally to room temperature. The mixture was then washed with N,N-dimethylformamide, filtered, and placed in a 60 °C forced-air drying oven. After drying for 16 hours, yellowish-brown crystals A were obtained.

[0069] Step 2: Place the yellowish-brown crystal A into a mortar and grind it to obtain yellowish-brown powder B.

[0070] Step 3: Weigh 0.125g of yellowish-brown powder B, 0.125g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 1g of polyethylene oxide (PEO) in a mass ratio of 1:1:8, add 20ml of N,N-dimethylformamide (DMF) solution, and stir at room temperature for 72 hours to obtain yellowish-brown viscous liquid C.

[0071] Step 4: Place the uniformly mixed yellowish-brown viscous liquid C in a vacuum drying oven at 60°C for 10 minutes to eliminate the formation of air bubbles inside the solvent. Then pour it into a polytetrafluoroethylene mold with dimensions of 10*10*0.5 cm and place it at room temperature for 12 hours to obtain a yellowish-brown polymer flexible diaphragm D.

[0072] Step 5: Cut the dried polymer film D into small circular pieces with a diameter of 19 mm to obtain polymer solid diaphragm sheet E, and place it in a glove box with a water oxygen value of less than 0.01 ppm.

[0073] Step 6, weigh 0.35g of LiNi 0.8 Mn 0.1 Co 0.1 O2, 1g of carbon black, and 0.05g of polyvinylidene fluoride (PVDF) in a mass ratio of 7:2:1 were placed in an agate mortar and ground thoroughly. An appropriate amount of N,N-2-methylpyrrolidone (NMP) was added, and the mixture was transferred to a small vial and stirred thoroughly with a magnetic stirrer for 36 hours to form a uniform, viscous black slurry F. The prepared black slurry F was coated onto aluminum foil using a 100-micron thick film scraper, vacuum dried at 60°C for 24 hours, and then cut into 12mm diameter slices to obtain LiNi. 0.8 Mn 0.1 Co 0.1 O2 electrode G;

[0074] Step 7, prepare LiNi 0.8 Mn 0.1 Co 0.1 The O2 electrode G, polymer solid-state separator E, and lithium anode were assembled into a CR2032 battery for subsequent performance testing. The battery was then assembled according to the positive electrode shell, LiNi... 0.8 Mn 0.1 Co 0.1 The O2 electrode G, the polymer solid diaphragm E dipped in electrolyte, the lithium sheet, the gasket, the spring sheet, and the negative electrode shell are assembled in sequence. The entire process is carried out in a glove box with a water oxygen value of less than 0.01 ppm.

[0075] like Figure 1 As shown, it is NH2 - A schematic diagram of the preparation process of hydrogen-bonded cross-linked quasi-solid-state hybrid lithium-ion battery separator material.

[0076] like Figure 2 The image shows the X-ray diffraction patterns of the precursor MOZ-201-NH2 crystal material and the standard anionic metal-organic zeolite framework material. The spectra reveal that the characteristic peak positions of the synthesized crystal are essentially consistent with those on the standard card.

[0077] like Figure 3 As shown, this is the NH2 prepared according to the present invention. - The current-voltage relationship of a hydrogen-bonded cross-linked quasi-solid-state hybrid lithium-ion battery at a scan rate of 0.01 mV / s is shown. Within the voltage range of 2.2–4.2 V, a pair of distinct redox peaks appear near 3.8 V and 3 V in the CV curve, indicating high electrochemical activity, easy reaction, and high capacity of the material.

[0078] like Figure 4 As shown, this is the NH2 prepared according to the present invention. - The electrochemical impedance spectroscopy (EIS) of a hydrogen-bonded cross-linked quasi-solid-state hybrid lithium-ion battery consists of two main parts. The graph shows that the semicircle diameter is smaller at high frequencies, indicating a lower Faraday charge transfer resistance (Rct) for this material. The straight line represents the low-frequency region.

[0079] like Figure 5 As shown, this is the NH2 prepared according to the present invention. - The current-time curve of a hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery is shown in the inset. The AC impedance spectra of the same battery before and after polarization are displayed. The calculated lithium-ion transference number is 0.78, which is higher than that of typical polymer electrolytes. This is due to the NH2... - This type of hydrogen-bonded cross-linked polymer solid membrane has superior specific surface area and porosity, which can accelerate the transport of lithium ions.

[0080] like Figure 6 As shown, it is NH2 - The hydrogen-bonded cross-linked quasi-solid-state hybrid lithium-ion battery separator material was tested. The efficiency versus specific capacity relationship was shown in the graph after 50 cycles at a 1C rated capacitance. After 50 cycles, the battery's discharge specific capacity was 124 mAh / g, and its coulombic efficiency remained around 100%. This is NH2. - This type of hydrogen-bonded cross-linked polymer solid-state separator has superior specific surface area and porosity, which can accelerate lithium-ion transport and help improve the cycle stability of quasi-solid-state polymer lithium-ion batteries.

[0081] The anionic metal-organic zeolite framework material prepared in this invention was blended with polyethylene oxide (PEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to obtain NH2. - Crosslinked quasi-solid-state hybrid lithium-ion battery separator material. We assembled it into a quasi-solid-state battery and conducted charge-discharge cycle, electrochemical impedance, and lithium-ion transference number tests at room temperature. High lithium-ion transference number and charge-discharge specific capacity were obtained. This material utilizes NH2... - The method of replacing traditional quasi-solid-state electrolyte membranes with cross-linked quasi-solid-state hybrid lithium-ion battery membranes provides a new approach for the application of MOF materials in the field of quasi-solid-state lithium battery electrolyte membranes at room temperature.

Claims

1. NH2 - A method for preparing a hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery separator, characterized in that... The specific steps are as follows: Step 1: Zinc salt, pentamethyltetrazole, and 5-aminoisophthalic acid are mixed in N,N-dimethylformamide. After adding 4-methylammonium hydroxide, the mixture is reacted at high temperature. After naturally cooling to room temperature, it is washed, filtered, and dried to obtain yellowish-brown crystals A. Step 2: Place the yellowish-brown crystal A into a mortar and grind it to obtain yellowish-brown powder B; Step 3: Weigh out yellowish-brown powder B, lithium bis(trifluoromethanesulfonyl)imide and polyethylene oxide, add N,N-dimethylformamide solution, and stir at room temperature to obtain yellowish-brown viscous liquid C; Step 4: Place the yellowish-brown viscous liquid C in a vacuum drying oven at 60°C for 10 minutes to eliminate the formation of internal bubbles; then pour it into a polytetrafluoroethylene mold and dry it in an oven for 12 hours to obtain a yellowish-brown polymer solid film D. Step 5: Cut the dried polymer solid film D into small round pieces to obtain polymer solid diaphragm sheet E, and place it in a glove box with a water oxygen value of less than 0.01 ppm.

2. The NH2 according to claim 1 - A method for preparing a hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery separator, characterized in that... In step 1, the zinc salt can be replaced by either zinc chloride or zinc nitrate hexahydrate; the molar ratio of the zinc salt, pentamethyltetrazole, and 5-aminoisophthalic acid is 1:1:1; the oven temperature is set at 100–160°C, the reaction time is between 24 and 60 hours, the drying temperature is between 50 and 80°C, and the drying time is between 10 and 18 hours.

3. The NH2 according to claim 1 - A method for preparing a hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery separator, characterized in that... In step 3, the mass ratio of yellowish-brown powder B, lithium bis(trifluoromethanesulfonyl)imide, and polyethylene oxide is 1:1:8, and the mixture is stirred at room temperature for no less than 48 hours.

4. The NH2 according to claim 1 - A method for preparing a hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery separator, characterized in that... In step 4, the dimensions of the polytetrafluoroethylene mold are 10*10*0.5 cm.

5. The NH2 according to claim 1 - A method for preparing a hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery separator, characterized in that... The diameter of the cut piece in step 5 is 19mm. 6.NH2 - A method for preparing a hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery, characterized in that... The specific operation steps of using the polymer solid membrane sheet E according to any one of claims 1-5 are as follows: Step 1: Weigh lithium iron phosphate, carbon black, and polyvinylidene fluoride (PVDF), place them in an agate mortar, and grind them thoroughly. Add N,N-2-methylpyrrolidone, transfer the mixture to a small bottle, and stir thoroughly with a magnetic stir bar to form a uniform and viscous black slurry F. Coat the prepared black slurry F onto aluminum foil using a scraper, vacuum dry it at 60°C for 24 hours, and cut it into thin slices to obtain lithium iron phosphate electrode sheets G. Step 2: The prepared lithium iron phosphate electrode G, the polymer solid membrane E dipped in electrolyte, and the lithium negative electrode are assembled into a CR2032 battery. The entire assembly process is carried out in a glove box with a water oxygen value of less than 0.01 ppm for subsequent performance testing.

7. The NH2 according to claim 6 - A method for preparing a hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery, characterized in that... In step 1, the mass ratio of lithium iron phosphate, carbon black, and polyvinylidene fluoride (PVDF) is 7:2:1, and the mixture is stirred at room temperature for at least 24 hours, using a scraper with a thickness of 100 micrometers. In step 2, the lithium iron phosphate electrode G can be made from LiNi... 0.8 Mn 0.1 Co 0.1 O2 is used instead.

8. The NH2 according to claim 6 - A method for preparing a hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery, characterized in that... The diameter of the sheet mentioned in step 1 is 12 mm.

9. The NH2 according to claim 6 - A method for preparing a hydrogen-bonded crosslinked quasi-solid-state hybrid lithium-ion battery, characterized in that... The electrolyte in step 2 is a mixture of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium nitrate, wherein the molar ratio of LiTFSI to lithium nitrate is 1:5.

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