CN112279233B - Cl - Doped epsilon-LiVOPO 4 Lithium fast ion conductor and liquid phase preparation method thereof - Google Patents

Cl - Doped epsilon-LiVOPO 4 Lithium fast ion conductor and liquid phase preparation method thereof Download PDF

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CN112279233B
CN112279233B CN202011175244.5A CN202011175244A CN112279233B CN 112279233 B CN112279233 B CN 112279233B CN 202011175244 A CN202011175244 A CN 202011175244A CN 112279233 B CN112279233 B CN 112279233B
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deionized water
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CN112279233A (en
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水淼
舒杰
任元龙
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Ningbo University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/455—Phosphates containing halogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
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    • 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

Abstract

Cl ‑ Doped epsilon-LiVOPO 4 The fast lithium ion conductor and the liquid phase preparation process features that: the stoichiometric formula is LiVO (PO) 4 ) 1‑x Cl 3x Wherein: x =0.05-0.10; by Cl ‑ Doping, reducing the acting force of conducting lithium ions and a crystal framework, greatly reducing the conducting activation energy of the lithium ions, and improving the activity capability and the conductivity of the lithium ions; in addition, the method is particularly beneficial to ensure that the reaction raw materials are more uniform through two calcining processes, and the obtained material has higher purity; the concentration of oxygen vacancies and defects in the material is increased by rapid room temperature cooling, which is beneficial to the conduction of lithium ions; through liquid phase synthesis, a multi-component auxiliary agent is adopted, so that the uniformity of each component of a reactant is improved, and a high-purity product is obtained; the measures ensure that the normal temperature lithium ion conductivity of the lithium fast ion conductor exceeds 5.10 ‑4 S/cm, which is very beneficial to the application of the lithium fast ion conductor.

Description

Cl - Doped epsilon-LiVOPO 4 Lithium fast ion conductor and liquid phase preparation method thereof
Technical Field
The invention relates to the field of manufacturing of solid lithium fast ion conductors.
Background
Fast ionic conductors, also known as superionic conductors, refer to a class of ionic conductors having an ionic conductivity (10) comparable to that of liquid electrolytes over a range of temperatures -6 S/cm) and low ion conductance activation energy (typically less than 0.4 eV). The fast ionic conductor has important application in the fields of electrode materials of energy storage batteries, gas detectors, solid electrolyte diaphragms, super-large capacity capacitors, timers, coulometers, electrochromic displays and the like.
The migration rate of carriers in the fast ion conductor is often far less than the charge transfer on the surface of the electrode and the ion diffusion rate in the electrode material, so that the rate control step in the whole electrode reaction kinetics is formed, and therefore, the development of the lithium fast ion conductor with higher lithium ion conductivity is the key point for developing high-performance application. In view of the current development status of lithium fast ion conductors: LLTO (Li, la) TiO 3 The fast ion conductor has high intragranular conductivity (at 10) -3 About S/cm) and relatively high total conductivity (10) at normal temperature -4 S/cm-10 -5 S/cm), but the LLTO decomposition voltage is low, and it cannot constitute an all-solid-state battery having a discharge voltage of 3.7V or more and is unstable to a metallic lithium negative electrode; liM having NASICON-type polycrystals 2 (PO 4 ) 3 (M = Ti, ge, zr) is a tetrahedron PO 4 And octahedron MO 6 Net composed ofThe frame structure generates holes on the structure and fillable coordination, so that a large amount of Li ions can be regulated and controlled, and the lithium ion conductive material is a promising high-lithium ion conductivity fast ion conductor. The ionic conductivity can be further improved by the substitution of aliovalent ions, by introducing holes or interstitial lithium ions into the structure [ Xiaooxing Xu, zhooyin Wen, zhonghuaGu, et al, solid State Ionics,171, 2004, 207-212.]. Such as Linzu 32405, li Shi Toona, etc. [ Linzu 32405, li Shi Toona, silicate academic newspaper, 9 (3), 1981, 253-257.]Discovered Li 1+x Ti 2- x Ga x P 3 O 12 ，Li 1+2x Ti 2-x MgxP 3 O 12 ， Li 1+x Ge 2-x CrxP 3 O 12 ，Li 1+x Ge 2-x Al x P 3 O 12 ，Li 1+x Ti 2-x In x P 3 O 12 Iso-systems or others, e.g. Li 1+2x+2y Al x Mg y Ti 2-x-y Si x P 3-x O 12 ，Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 ，Li 1+x Al x Ti 2-x P 3 O 12 The systems have higher lithium ion conductivity. However, these systems generally have a lithium ion conductivity of 10 at room temperature -4 S/cm-10 -6 The requirement of non-thin film lithium ion batteries on the electrolyte conductivity cannot be well met between S/cm. A new type of Li ion fast ion conductor is reported in the journal of Germany applied chemistry by Ramaswamy Murugan, 2007 7 La 3 Zr 2 O 12 Its lithium ion conductivity at normal temperature exceeds 1X 10 -4 S·cm -1 The decomposition voltage exceeds 5.5V, the lithium metal can be used as a negative electrode, the lithium Fast ion solid electrolyte material is stable to air and moisture, and the lithium Fast ion solid electrolyte material has great application potential (Ramasuman Murugan, venkataraman Thangidurai, werner Weppner, (2007).' Fast lithium ion reduction in garnet-type Li 7 La 3 Zr 2 O 12 "Angewandte Chemie-International Edition 46 (41): 7778-7781.). However, in the case of higher current requirementsTo achieve 5.0X 10 -4 The requirement of normal operation of the battery can be met only by about S/cm, and in addition, the synthesis temperature of the fast ion conductor is about 1350 ℃, the temperature is high, and the energy consumption is high.
Therefore, screening of the fast lithium ion conductor material with high normal temperature conductivity, relatively simple preparation and low synthesis temperature is the premise of industrialization of the fast lithium ion conductor.
Disclosure of Invention
The invention aims to solve the technical problem of providing Cl in the prior art - Doped epsilon-LiVOPO 4 A lithium fast ion conductor and a liquid phase preparation method thereof. Epsilon-LiVOPO 4 Is LiVOPO 4 The triclinic type can be used as a positive electrode material of a lithium ion battery. By Cl in the invention - Doping, reducing the acting force of the conductive lithium ions and the crystal framework, greatly reducing the conductive activation energy of the lithium ions, improving the activity capability and the conductivity of the lithium ions, and ensuring that the normal-temperature lithium ion conductivity of the lithium fast ion conductor exceeds 5.10 -4 S/cm, so that the lithium ion conductive material can be used as a lithium fast ion conductor with excellent performance and is closer to the lithium ion conductivity of a liquid electrolyte; meanwhile, liquid phase synthesis is adopted, and multi-component auxiliaries are adopted, so that the uniformity of each component of the reactant is improved, and a high-purity product is obtained.
The invention is achieved by the following technical scheme that the normal-temperature lithium ion conductivity exceeds 5 & 10 -4 S/cm of lithium fast ion conductor with the stoichiometric formula LiVO (PO) 4 ) 1-x Cl 3x Wherein: x =0.05-0.10.
In this embodiment, liVO (PO) will be used 4 ) 1-x Cl 3x Wherein: x =0.05-0.10, stoichiometric molar ratio of solid LiNO 3 、NH 4 H 2 PO 4 、LiCl、V 2 O 5 And 6 times of V 2 O 5 Uniformly mixing oxalic acid in mole number, adding deionized water while strongly stirring until all solid substances are dissolved, recording the mass of the added deionized water, continuously adding deionized water with the mass 1.0-1.5 times of the recorded mass of the deionized water, and uniformly stirringMixing and recording the solution as I; mixing an auxiliary agent A with the mole number of 3 times that of chlorine in the solution I and an auxiliary agent B with the mole number of 2 times that of chlorine in the solution I, adding ammonia water containing ammonia with the mole number of 10 times that of chlorine in the solution I while strongly stirring until all solid substances are dissolved, recording the mass of the added deionized water again, continuously adding deionized water with the mass of 3-5 times that of the recorded deionized water, uniformly stirring, and recording that the solution is II; adding the solution II into the solution I rapidly and totally under strong stirring, raising the temperature of the system to 30-50 ℃ and maintaining stirring at the temperature for 20-50 minutes, adding the auxiliary C in an amount which is 30-50 times that of the auxiliary A, simultaneously adding 6g of acrylamide/100 mL of water and 1g of N, N' -dimethyl bisacrylamide/100 mL of water, stirring for 5-15 minutes at a speed of 1500-2000 rpm by using a polytetrafluoroethylene stirring paddle, then raising the temperature to 75-85 ℃ at a speed of 5-10 ℃/minute and keeping the temperature until the gel is in a jelly state. Drying the formed gel in a low-temperature high-vacuum environment, wherein a finished product freeze dryer on the market can be adopted in the drying process, the gel is placed in a sample plate of the freeze dryer, a refrigerating machine is started, a vacuum pump is started to improve the vacuum degree when the temperature of the gel on the sample plate is reduced to-45 to-50 ℃, the air pressure in a system is reduced to be below 25-35Pa, a clapboard is started to control the temperature to start dehydration and drying, other operation parameters adopt preset values of the machine, the gel is taken out and ground again in an agate grinding bowl for 10-30 minutes after the air pressure in the system is stably dried, the ground powder is heated to 500-550 ℃ at the speed of 5-30 ℃/minute in the air atmosphere and is cooled along with the furnace after the temperature is kept for 10-20 hours; grinding the cooled powder in an agate grinding bowl for 10-30 minutes again, heating the ground powder to 600-650 ℃ at the speed of 5-15 ℃/minute in the air atmosphere, preserving the heat for 10-20 hours, then rapidly taking out the powder and cooling the powder in argon at room temperature; thereafter, after grinding, in a press at 1X 10 7 Pa-8×10 7 Pressing into slices under the pressure of Pa, putting the slices into a tube furnace, heating to 500-550 ℃ at the speed of 5-10 ℃/min in the oxygen atmosphere of 10-60Pa, preserving the heat for 5-10 hours, and cooling along with the furnace; the lithium fast ion conductor sheet was produced.
The assistant A is a compound with a plurality of carboxyl groups and tertiary nitrogen atoms in a molecular structure, and is one of ethylenediamine tetraacetic acid and nitrilotriacetic acid; the assistant B is a water-soluble compound with polyhydroxy in the molecular structure but without carboxyl, and comprises but is not limited to ethylene glycol and glycerol; the assistant C is a compound which is easy to polymerize and contains a carbon-carbon double bond and a hydroxyl group or a carboxyl group in a water-soluble molecular structure, and comprises but is not limited to acrylic acid and methacrylic acid;
the composition is LiVO (PO) as shown in FIG. 1 4 ) 0.95 Cl 0.15 The XRD pattern of the lithium fast ion conductor has pure phase and no impurity phase, and the conductivity is 6.3.10 determined by electrochemical impedance spectroscopy -4 S/cm。
Compared with the prior art, the invention has the advantages that: by Cl - Doping, so that the acting force of conducting lithium ions and a crystal framework is reduced, the conducting activation energy of the lithium ions is greatly reduced, and the activity capacity and the conductivity of the lithium ions are improved; in addition, the method is particularly beneficial to ensure that the reaction raw materials are more uniform through two calcining processes, and the obtained material has higher purity; the concentration of oxygen vacancies and defects in the material is increased by rapid room temperature cooling, which is beneficial to the conduction of lithium ions; through liquid phase synthesis, a multi-component auxiliary agent is adopted, so that the uniformity of each component of a reactant is improved, and a high-purity product is obtained; the measures ensure that the normal temperature lithium ion conductivity of the lithium fast ion conductor exceeds 5-10 -4 S/cm, which is very beneficial to the application of the lithium fast ion conductor.
Drawings
FIG. 1 shows a composition of LiVO (PO) 4 ) 0.95 Cl 0.15 XRD pattern of lithium fast ion conductor.
FIG. 2 shows a composition of LiVO (PO) 4 ) 0.95 Cl 0.15 The electrochemical impedance spectrum of the lithium fast ion conductor at 300, 400, 500 and 600K can be calculated to obtain the ionic conductivity.
FIG. 3 shows a composition of LiVO (PO) 4 ) 0.95 Cl 0.15 Calculating the inverse relation graph of logarithmic ion conductivity and temperature at 300, 400, 500 and 600K of the lithium fast ion conductor to obtain the activation of ion migrationThe energy is 0.42eV.
Detailed Description
The present invention is described in further detail below with reference to examples.
Example 1: will be according to LiVO (PO) 4 ) 0.95 Cl 0.15 Stoichiometric molar ratio of solid LiNO 3 、NH 4 H 2 PO 4 、LiCl、 V 2 O 5 And 6 times of V 2 O 5 Uniformly mixing oxalic acid with molar number, adding deionized water while strongly stirring until all solid substances are dissolved, recording the mass of the added deionized water, continuously adding deionized water with the mass 1.0 time of the recorded mass of the deionized water, uniformly stirring, and recording the solution as I; mixing ethylene diamine tetraacetic acid with the mole number of 3 times of that of chlorine in the solution I and ethylene glycol with the mole number of 2 times of that of chlorine in the solution I, adding ammonia water containing ammonia with the mole number of 10 times of that of chlorine in the solution I while strongly stirring until all solid substances are dissolved, recording the mass of the added deionized water again, continuously adding deionized water with the mass of 3 times of that of the recorded deionized water, uniformly stirring, and recording that the solution is II; solution II was added all at once to solution I with vigorous stirring, the temperature of the system was raised to 30 ℃ and stirring was maintained at this temperature for 20 minutes, then acrylic acid in an amount 30 times that of the substance ethylenediaminetetraacetic acid was added, while acrylamide in an amount of 6g acrylamide/100 mL water and N, N '-dimethylbisacrylamide in an amount of 1g N, N' -dimethylbisacrylamide/100 mL water were added, and after stirring for 5 minutes with a Teflon stirring paddle at 1600rpm, it was raised to 75 ℃ at a rate of 6 ℃/min and the temperature was maintained until it became a jelly-like gel. Drying the formed gel in low-temperature high-vacuum environment, wherein the drying process can adopt a finished product freeze dryer on the current market, putting the gel into a sample tray of the freeze dryer, starting a refrigerating machine, controlling the temperature of the gel on the sample tray to be-45 ℃, starting a vacuum pump to improve the vacuum degree, controlling the temperature of a partition plate to be dehydrated and dried when the gas pressure in a system is reduced to be below 25Pa, adopting machine preset values as other operating parameters, and taking out the gel after the stable drying of the gas pressure in the system is finishedGrinding again for 12 minutes in an agate grinding bowl, heating the ground powder to 500 ℃ at the speed of 6 ℃/minute in the air atmosphere, preserving the heat for 10 hours, and then cooling along with the furnace; grinding the cooled powder in an agate grinding bowl for 10 minutes again, heating the ground powder to 610 ℃ at the speed of 7 ℃/minute in an air atmosphere, preserving the heat for 10 hours, then quickly taking out the powder, and cooling the powder in argon at room temperature; thereafter, after grinding, in a press at 1X 10 7 Pressing the sheet under the pressure of Pa, putting the prepared sheet into a tubular furnace, heating the sheet to 500 ℃ at the speed of 6 ℃/min in the oxygen atmosphere of 10Pa, preserving the heat for 6 hours, and then cooling the sheet along with the furnace; the lithium fast ion conductor sheet was produced.
Example 2: will be according to LiVO (PO) 4 ) 0.9 Cl 0.3 Stoichiometric molar ratio of solid LiNO 3 、NH 4 H 2 PO 4 、LiCl、 V 2 O 5 And 6 times of V 2 O 5 Uniformly mixing oxalic acid in mole number, adding deionized water while strongly stirring until all solid substances are dissolved, recording the mass of the added deionized water, then continuously adding deionized water with the mass 1.5 times of the recorded mass of the deionized water, uniformly stirring, and recording the solution as I; mixing nitrilotriacetic acid with the mole number of 3 times that of chlorine in the solution I and glycerol with the mole number of 2 times that of chlorine in the solution I, adding ammonia water containing ammonia with the mole number of 10 times that of chlorine in the solution I while strongly stirring until all solid substances are dissolved, recording the mass of the added deionized water again, then continuously adding deionized water with the mass 5 times that of the recorded deionized water, uniformly stirring, and recording the solution as II; solution II was added all at once to solution I with vigorous stirring, the temperature of the system was raised to 50 ℃ and stirring was maintained at this temperature for 50 minutes, then methacrylic acid in an amount 50 times that of the nitrilotriacetic acid species was added, along with acrylamide in an amount of 6g acrylamide per 100mL and N, N '-dimethylbisacrylamide in an amount of 1g N, N' -dimethylbisacrylamide per 100mL, and after stirring for 15 minutes with a Teflon stirring paddle at 2000rpm, it was raised to 85 ℃ at a rate of 10 ℃/minute and the temperature was maintained until it became a jelly-like gel. Subjecting the formed gel to high fidelity at low temperatureDrying in a hollow environment, wherein a finished product freeze dryer on the current market can be adopted in the drying process, the gel is placed in a sample plate of the freeze dryer, a refrigerating machine is started, when the temperature of the gel on the sample plate is reduced to-50 ℃, a vacuum pump is started to improve the vacuum degree, when the gas pressure in the system is reduced to below 35Pa, a clapboard is started to control the temperature to begin dehydration and drying, other operation parameters adopt preset values of the machine, after the stable drying of the gas pressure in the system is finished, the gel is taken out and ground in an agate grinding bowl for 30 minutes again, and the ground powder is heated to 550 ℃ at the speed of 30 ℃/minute in the air atmosphere and is cooled along with the furnace after being kept warm for 18 hours; grinding the cooled powder in an agate grinding bowl for 30 minutes again, heating the ground powder to 640 ℃ at the speed of 15 ℃/minute in an air atmosphere, preserving the heat for 18 hours, taking out the powder quickly, and cooling the powder in argon at room temperature; thereafter, after grinding, in a press at 8X 10 7 Pressing the sheet under the pressure of Pa, putting the prepared sheet into a tubular furnace, heating the sheet to 550 ℃ at the speed of 10 ℃/min in the oxygen atmosphere of 60Pa, preserving the heat for 10 hours, and then cooling the sheet along with the furnace; the lithium fast ion conductor sheet was produced.
Example 3: will be according to LiVO (PO) 4 ) 0.93 Cl 0.21 Wherein: x =0.05-0.10, stoichiometric molar ratio of solid LiNO 3 、 NH 4 H 2 PO 4 、LiCl、V 2 O 5 And 6 times of V 2 O 5 Uniformly mixing oxalic acid in mole number, adding deionized water while strongly stirring until all solid substances are dissolved, recording the mass of the added deionized water, then continuously adding deionized water with the mass 1.2 times of the recorded mass of the deionized water, uniformly stirring, and recording the solution as I; mixing nitrilotriacetic acid 3 times of the chlorine mole number in the solution I and glycerol 2 times of the chlorine mole number in the solution I, adding ammonia water containing ammonia 10 times of the chlorine mole number in the solution I into the mixture while strongly stirring until all solid substances are dissolved, recording the mass of the added deionized water again, then continuously adding deionized water 4 times of the recorded mass of the deionized water, uniformly stirring the mixture, and recording the solution as II; adding solution II into solution I under strong stirring, and increasing the temperature of the systemAfter stirring at 40 ℃ for 35 minutes at this temperature, acrylic acid in an amount 40 times that of the nitrilotriacetic acid species was added, along with acrylamide in an amount of 6g acrylamide per 100mL and N, N '-dimethylbisacrylamide in an amount of 1g N, N' -dimethylbisacrylamide per 100mL were added, and after stirring at 1500rpm for 10 minutes using a polytetrafluoroethylene paddle, the mixture was raised to 80 ℃ at a rate of 5 ℃/min and the temperature was maintained until it became a jelly-like gel. Drying the formed gel in a low-temperature high-vacuum environment, wherein a finished product freeze dryer on the market can be adopted in the drying process, the gel is placed in a sample disc of the freeze dryer, a refrigerating machine is started, when the temperature of the gel on the sample disc is reduced to-47 ℃, a vacuum pump is started to improve the vacuum degree, when the gas pressure in a system is reduced to be below 30Pa, a clapboard is started to control the temperature to start dehydration and drying, other operation parameters adopt preset values of the machine, after the stable drying of the gas pressure in the system is finished, the gel is taken out and ground in an agate grinding bowl for 10 minutes again, and the ground powder is heated to 520 ℃ at the speed of 5 ℃/minute in the air atmosphere and is cooled along with the furnace after being kept warm for 15 hours; grinding the cooled powder in an agate grinding bowl for 20 minutes again, heating the ground powder to 600 ℃ at the speed of 5 ℃/minute in the air atmosphere, preserving the temperature for 10 hours, and then rapidly taking out the powder and cooling the powder in argon at room temperature; thereafter, after grinding, in a press at 5X 10 7 Pressing the sheet under the pressure of Pa, putting the prepared sheet into a tubular furnace, heating the sheet to 520 ℃ at the speed of 5 ℃/min in the oxygen atmosphere of 40Pa, preserving the temperature for 5 hours, and then cooling the sheet along with the furnace; the lithium fast ion conductor sheet was produced.
Example 4: will be according to LiVO (PO) 4 ) 0.94 Cl 0.18 Stoichiometric molar ratio of solid LiNO 3 、NH 4 H 2 PO 4 、LiCl、 V 2 O 5 And 6 times of V 2 O 5 Uniformly mixing oxalic acid with molar number, adding deionized water while strongly stirring until all solid substances are dissolved, recording the mass of the added deionized water, continuously adding deionized water with the mass 1.1 times of the recorded mass of the deionized water, uniformly stirring, and recording the solution as I; adding 2 times of EDTA 3 times of the mole number of chlorine in the solution IMixing and adding ammonia water containing ammonia 10 times of the mole number of chlorine in the solution I into glycerol in the solution I, adding deionized water while strongly stirring until all solid substances are dissolved, recording the mass of the added deionized water again, continuously adding deionized water 5 times of the mass of the recorded deionized water, uniformly stirring, and recording the solution as II; the solution II was rapidly added to the solution I in its entirety under vigorous stirring, the temperature of the system was raised to 50 ℃ and after maintaining stirring at this temperature for 50 minutes, methacrylic acid in an amount 35 times that of the substance ethylenediaminetetraacetic acid was added, along with acrylamide in an amount of 6g acrylamide per 100mL water and N, N '-dimethylbisacrylamide in an amount of 1gN, N' -dimethylbisacrylamide per 100mL water, and after stirring for 10 minutes at 2000rpm using a polytetrafluoroethylene paddle, it was raised to 82 ℃ at 7 ℃/minute and the temperature was maintained until it became a jelly-like gel. Drying the formed gel in a low-temperature high-vacuum-degree environment, wherein a finished product freeze dryer on the current market can be adopted in the drying process, the gel is placed in a sample tray of the freeze dryer, a refrigerating machine is started, when the temperature of the gel on the sample tray is reduced to-45 ℃, a vacuum pump is started to improve the vacuum degree, when the gas pressure in the system is reduced to be below 30Pa, a clapboard is started to control the temperature to start dehydration and drying, other operation parameters adopt preset values of the machine, after the stable drying of the gas pressure in the system is finished, the gel is taken out and ground in an agate grinding bowl for 20 minutes again, and the ground powder is heated to 510 ℃ at the speed of 20 ℃/minute in the air atmosphere, is kept warm for 20 hours and then is cooled along with the furnace; grinding the cooled powder in an agate grinding bowl for 10 minutes again, heating the ground powder to 650 ℃ at the speed of 10 ℃/minute in the air atmosphere, preserving the temperature for 20 hours, then rapidly taking out the powder, and cooling the powder in argon at room temperature; thereafter, after grinding, in a press at 5X 10 7 Pressing the sheet under the pressure of Pa, putting the prepared sheet into a tubular furnace, heating the sheet to 520 ℃ at the speed of 5 ℃/min in the oxygen atmosphere of 50Pa, preserving the temperature for 7 hours, and then cooling the sheet along with the furnace; the lithium fast ion conductor sheet was produced.
Example 5: will be according to LiVO (PO) 4 ) 0.92 Cl 0.24 Stoichiometric molar ratio of solid LiNO 3 、NH 4 H 2 PO 4 、LiCl、 V 2 O 5 And 6 times of V 2 O 5 Uniformly mixing oxalic acid with molar number, adding deionized water while strongly stirring until all solid substances are dissolved, recording the mass of the added deionized water, continuously adding deionized water with the mass 1.5 times of the recorded mass of the deionized water, uniformly stirring, and recording the solution as I; mixing nitrilotriacetic acid 3 times of the mole number of chlorine in the solution I and mannitol 2 times of the mole number of chlorine in the solution I, adding ammonia water containing ammonia 10 times of the mole number of chlorine in the solution I while strongly stirring until all solid substances are dissolved, recording the mass of the added deionized water again, continuously adding deionized water 4 times of the recorded mass of the deionized water, uniformly stirring and recording the solution as II; the solution II was rapidly added to the solution I in its entirety under vigorous stirring, the temperature of the system was raised to 40 ℃ and stirring was maintained at this temperature for 20 minutes, then methallyl alcohol in an amount 30 times the amount of nitrilotriacetic acid species was added, simultaneously with acrylamide in an amount of 6g acrylamide per 100mL and N, N '-dimethylbisacrylamide in an amount of 1gN, N' -dimethylbisacrylamide per 100mL, stirred with a Teflon stirring paddle at 2000rpm for 10 minutes and then raised to 85 ℃ at a speed of 7 ℃/min and the temperature was maintained until a jelly-like gel was formed. Drying the formed gel in a low-temperature high-vacuum environment, wherein a finished product freeze dryer on the market can be adopted in the drying process, the gel is placed in a sample disc of the freeze dryer, a refrigerating machine is started, when the temperature of the gel on the sample disc is reduced to-50 ℃, a vacuum pump is started to improve the vacuum degree, when the gas pressure in a system is reduced to be lower than 35Pa, a clapboard is started to control the temperature to start dehydration and drying, other operation parameters adopt preset values of the machine, after the stable drying of the gas pressure in the system is finished, the gel is taken out and ground in an agate grinding bowl for 30 minutes again, and the ground powder is heated to 550 ℃ at the speed of 30 ℃/minute in the air atmosphere and is cooled along with the furnace after being kept warm for 15 hours; grinding the cooled powder in an agate grinding bowl for 20 minutes again, heating the ground powder to 620 ℃ at the speed of 10 ℃/minute in the air atmosphere, preserving the temperature for 15 hours, then rapidly taking out the powder and putting the powder in argon at room temperatureCooling; thereafter, after grinding, in a press at 3X 10 7 Pressing the sheet under the pressure of Pa, putting the prepared sheet into a tubular furnace, heating the sheet to 520 ℃ at the speed of 7 ℃/min in the oxygen atmosphere of 50Pa, preserving the heat for 8 hours, and then cooling the sheet along with the furnace; the lithium fast ion conductor sheet was produced.

Claims (1)

1. Cl - Doped epsilon-LiVOPO 4 Lithium fast ion conductor, characterized by: the stoichiometric formula is LiVO (PO) 4 ) 1- x Cl 3x Wherein: x =0.05-0.10; normal temperature lithium ion conductivity over 5.10 -4 S/cm; the preparation process comprises the following steps of preparing LiVO (PO) 4 ) 1-x Cl 3x Wherein: x =0.05-0.10, stoichiometric molar ratio of solid LiNO 3 、NH 4 H 2 PO 4 、LiCl、V 2 O 5 And 6 times of V 2 O 5 Uniformly mixing oxalic acid in mole number, adding deionized water while strongly stirring until all solid substances are dissolved, recording the mass of the added deionized water, then continuously adding deionized water with the mass 1.0-1.5 times of the recorded mass of the deionized water, uniformly stirring, and recording the solution as I; mixing and adding ammonia water containing ammonia of which the mole number is 10 times that of the chlorine in the solution I into the assistant A of which the mole number is 3 times that of the chlorine in the solution I and the assistant B of which the mole number is 2 times that of the chlorine in the solution I while strongly stirring until all solid substances are dissolved, recording the mass of the added deionized water again, continuously adding deionized water of which the mass is 3-5 times that of the recorded deionized water, uniformly stirring, and recording the solution as II; adding the solution II into the solution I rapidly and totally under strong stirring, raising the temperature of the system to 30-50 ℃ and maintaining stirring at the temperature for 20-50 minutes, adding the auxiliary C in an amount which is 30-50 times that of the auxiliary A, simultaneously adding 6g of acrylamide/100 mL of water and 1g of N, N' -dimethyl bisacrylamide/100 mL of water, stirring for 5-15 minutes at a speed of 1500-2000 rpm by using a polytetrafluoroethylene stirring paddle, then raising the temperature to 75-85 ℃ at a speed of 5-10 ℃/minute and keeping the temperature until the gel is in a jelly state; will formThe gel is dried in the environment with low temperature and high vacuum degree, the drying process adopts a finished product freeze dryer on the current market, the gel is put into a sample plate of the freeze dryer, a refrigerator is started, when the temperature of the gel on the sample plate is reduced to-45 to-50 ℃, a vacuum pump is started to improve the vacuum degree, when the gas pressure in the system is reduced to below 25-35Pa, a clapboard is started to control the temperature and begin dehydration drying, other operation parameters adopt preset values of the machine, after the stable drying of the gas pressure in the system is finished, the gel is taken out and ground again in an agate grinding bowl for 10-30 minutes, the ground powder is heated to 500-550 ℃ at the speed of 5-30 ℃/minute in the air atmosphere and is cooled along with the furnace after heat preservation for 10-20 hours; grinding the cooled powder in an agate grinding bowl for 10-30 minutes again, heating the ground powder to 600-650 ℃ at the speed of 5-15 ℃/minute in the air atmosphere, preserving the temperature for 10-20 hours, and then rapidly taking out the powder and cooling the powder in argon at room temperature; thereafter, after grinding, in a press at 1X 10 7 Pa-8×10 7 Pressing into slices under the pressure of Pa, putting the slices into a tube furnace, heating to 500-550 ℃ at the speed of 5-10 ℃/min in the oxygen atmosphere of 10-60Pa, preserving the heat for 5-10 hours, and cooling along with the furnace; preparing the lithium fast ion conductor slice;
the assistant A is a compound with a plurality of carboxyl groups and tertiary nitrogen atoms in a molecular structure, and is one of ethylenediamine tetraacetic acid and nitrilotriacetic acid; the assistant B is a water-soluble compound which has polyhydroxy in a molecular structure and does not contain carboxyl, and is one of ethylene glycol and glycerol; the assistant C is a compound which is easy to polymerize and contains carbon-carbon double bonds and hydroxyl or carboxyl in a water-soluble molecular structure, and is one of acrylic acid and methacrylic acid.
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