CN106876680A - A kind of continuous conduction original position C/Ag, Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries and preparation method thereof - Google Patents

A kind of continuous conduction original position C/Ag, Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries and preparation method thereof Download PDF

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Publication number
CN106876680A
CN106876680A CN201710213007.5A CN201710213007A CN106876680A CN 106876680 A CN106876680 A CN 106876680A CN 201710213007 A CN201710213007 A CN 201710213007A CN 106876680 A CN106876680 A CN 106876680A
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copper
lithium
aqueous solution
copper fluoride
original position
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姘存芳
水淼
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Ningbo Kyrgyzstan Xin New Mstar Technology Ltd
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Ningbo Kyrgyzstan Xin New Mstar Technology Ltd
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    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/582—Halogenides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A kind of continuous conduction original position C/Ag, Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries and preparation method thereof; the method is by the drying process and the carbonization under gas shield and in-situ reducing process under low temperature, high vacuum condition; form the continuous carbon film with hole and gap structure; and fixation forms copper fluoride and the surface in situ in copper fluoride particle restores a certain amount of metallic copper and silver on the carbon film, plays the electronic conductivity for increasing substantially composite；For electrode material provides homogeneity crystallization nuclei in electric discharge, the dynamics for reducing New phase formation hinders；Improve the speed of exoelectrical reaction；Also avoid simultaneously and the side reaction products such as various double salt of copper fluoride are generated in liquid phase reactor and with excellent chemical property.

Description

A kind of continuous conduction original position C/Ag, Cu/CuF2Compound copper fluoride lithium ion cell positive Material and preparation method thereof
Technical field
The present invention relates to a kind of high-performance copper fluoride complex lithium electricity positive electrode manufacture method technical field.
Background technology
Lithium rechargeable battery has volume, weight energy higher than high, voltage, low self-discharge rate, memory-less effect, circulation Long lifespan, the power density definitely advantage such as high, at present global portable power source market have more than 30,000,000,000 dollar/year shares and with Speed more than 10% gradually increases.Particularly in recent years, petering out with fossil energy, solar energy, wind energy, biomass The new energy such as energy are increasingly becoming the alternative of traditional energy, and wherein wind energy, solar energy has intermittence, to meet lasting electricity Power supply needs to use substantial amounts of energy-storage battery simultaneously；The urban air-quality problem that vehicle exhaust brings is increasingly serious, electronic Very urgent stage has been arrived in vigorously advocating and developing for car (EV) or hybrid electric vehicle (HEV)；These demands are provided Lithium ion battery explosive growth point, while also the performance to lithium ion battery proposes requirement higher.
The raising of the capacity of anode material for lithium-ion batteries is the primary goal of scientific and technical personnel's research, high power capacity positive electrode Research and development can to alleviate current Li-ion batteries piles volume big, heavy weight, price high-leveled and difficult to meet power consumption high and high-power equipment The situation of needs.But since lithium ion battery in 1991 is commercialized, the actual specific capacity of positive electrode is hovered all the time Between 100-180mAh/g, the low bottleneck for having become lifting lithium ion battery specific energy of positive electrode specific capacity.It is commercial at present The most commonly used practical positive electrode of lithium ion battery be LiCoO2, the theoretical specific capacity of cobalt acid lithium is 274mAh/g, and Actual specific capacity is between 130-140mAh/g, and cobalt is strategic materials, expensive and have larger toxicity.Therefore in recent years Come, the researcher of countries in the world is devoted to the research and development of Olivine-type Cathode Material in Li-ion Batteries always, to current, screening Up to tens of kinds of the lithium ion cell positive for going out, but really have potential commercial applications prospect or be already present in the market just Pole material is really very few.Such as lithium manganate having spinel structure LiMn2O4, its cost is relatively low, is easier to prepare, security performance It is relatively good, but capacity is relatively low, theoretical capacity is 148mAh/g, and actual capacity is in 100-120mAh/g, and the material capacity Circulation holding capacity it is not good, under high temperature capacity attenuation quickly, Mn3+John-Teller effects and dissolving in the electrolyte it is long Researcher has been annoying since phase.The LiNiO of layer structure2And LiMnO2Although having larger theoretical specific capacity, respectively 275mAh/g and 285mAh/g, but they prepare extremely difficult, and heat endurance is poor, and cyclicity is very poor, and capacity attenuation is quickly.And Progressively commercialized LiFePO4 LiFePO at present4Low cost, heat endurance are good, environment-friendly, but its theoretical capacity About only have 170mAh/g, and actual capacity 140mAh/g or so [Chun S Y, Bloking J T, Chiang Y M, Nature Materials, 2002,1：123-128.].There is the positive pole material more than 200mAh/g specific capacities of market prospects at present Material only has lithium vanadate Li1+xV3O8, Li1+xV3O8Material can have the capacity possessed even close to 300mAh/g, but the average electricity of its electric discharge Often toxicity is larger for barium oxide in pressing relatively low and production process.Lithium high is than on positive electrode in recent years, particularly manganese base manganese- The lithium high of nickel binary and manganese base manganese-nickel-cobalt ternary solid solution system than positive electrode, with the Capacity Ratio more than 200mAh/g, compared with Heat endurance high and the cost of relative moderate and paid close attention to by people, but the performance under the material high magnification is paid no attention to very much Think, limit its application [Young-Sik Hong, Yong Joon Park, et al., Solid in electrokinetic cell State Ionics, 2005,176：1035-1042].
In recent years, fluoride positive electrode enters the visual field of researcher because its capacity is high, the prices of raw materials are low.Fluorine Compound material is different with the operation principle of conventional lithium ion battery positive electrode, traditional lithium ion cell positive and negative pole All exist lithium ion can be embedded in or deintercalation space, and lithium ion in electrolyte it is embedded back and forth between a positive electrode and a negative electrode and Deintercalation and " rocking chair " battery proposed as Armand etc. that discharges.And fluoride is then a kind of transition material, that is, whole In individual discharge process, although Me has nothing in common with each other, MeFnCan occur similar following change [Badway F, Cosandey F, Pereira N, et al., Electrodes for Li Batteries, J.Electrochem.Soc., 2003,150 (10)： A1318-A1327.]：
nLi++MeFn+ne-→nLiF+Me0
Can discharge in this process and exceed well over 200mAh.g-1Specific capacity, thus it is high to obtain investigation of materials personnel The attention of degree.Such as fluorination iron material has had many document reports, however fluoride positive electrode often discharge curve does not have There is obvious platform, average discharge volt is low, energy density and power ratio are relatively low, such as be fluorinated the averaged discharge current potential of iron material At 2.0 volts or so.But fluorination copper product has the discharge platform voltage of about 3.2V, all there is average voltage high and that capacity is big is excellent Point.But it is also considerably less as the report of anode material for lithium-ion batteries on fluorination copper product, main difficulty is that fluorination The chemical property of copper has close contact and poor repeatability with preparation process；Meanwhile, fluorination copper product is in organic electrolyte Stability is also inadequate；It is exactly extremely low electronic conductivity that it also has a negative characteristic, therefore can be caused in charge and discharge process Polarizing voltage very high, although have researcher and the electrical conductivity of material is improved using carbon black mixing and ball milling is added, but graininess Carbon black be still difficult to form complete electrically conductive links, increase substantially its electronic conductivity.Finally, the material is produced in electric discharge Raw metallic copper and lithium fluoride cenotype, cenotype small particles in the stage that originally forms being kinetically on a sticky wicket, therefore to it Charge/discharge capacity afterwards, discharge potential, the holding capacity of charge/discharge capacity can have a negative impact.
Therefore exploitation one kind has complete conductive link, purity is high, technical process is environment-friendly, product quality is stable, tool The compound copper fluoride material preparation method for having excellent electrochemical performance is the key for being fluorinated copper product as secondary cell application.
The content of the invention
The present invention proposes a kind of continuous conduction original position C/Ag, Cu/CuF for existing background technology2Compound copper fluoride lithium Ion battery positive electrode and preparation method thereof, the method is consolidated copper nitrate by the drying process under low temperature, high vacuum condition It is scheduled in the Continuous Polyacrylamide body for maintaining hole and gap structure and copper material is fluorinated by liquid phase reactor in-situ preparation Material, the Continuous Polyacrylamide with hole and gap structure is integrally transformed into hole in heat treatment process thereafter and The continuous carbon film of gap structure, the continuous carbon film structure has high conductive capability, increases substantially the electronics of composite Electrical conductivity；The surface reduction in copper fluoride particle in heat treatment process goes out a certain amount of metallic copper and silver simultaneously, and metallic copper is Electrode material provides homogeneity crystallization nuclei in electric discharge, and the dynamics for reducing New phase formation hinders, and improves the appearance of material Amount, circulation volume stability and discharge platform current potential；Silver is favorably improved exoelectrical reaction speed.By the fixation of reaction raw materials Change, it is thus also avoided that the side reaction products such as various double salt of copper fluoride are generated in liquid phase reactor and there is excellent electrochemistry Energy.
This continuous conduction original position C/Ag, Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries and preparation method thereof, It is characterized by：It is 5-15wt% copper nitrates, 6-12wt% acrylamides, 1-2wt%N, N to prepare composition '-methylene bisacrylamide acyl The quality of the starting aqueous solution of amine, wherein acrylamide is N, 6 times of N '-methylene-bisacrylamide quality, uses polytetrafluoro Ethene agitating paddle is stirred 5-15 minutes with the speed of 900rpm-1200rpm.By the starting aqueous solution with 5-10 DEG C/min of speed Degree rises to 75-85 DEG C and keeps the temperature until starting aqueous solution is as gelatin gel.The gel that will be formed is in low temperature Dried in the environment of condition of high vacuum degree, can be put into for gel using finished product freeze drier in the market by the drying process Start refrigeration machine in freeze drier sample disc, treat that gelling temp is reduced to subzero 50 DEG C of subzero 45- in sample disc, opens vacuum Pump improves vacuum, treats that gas pressure is reduced to below 25-35Pa in system, opens baffle temperature control and starts to dehydrate, Other operating parameters take machine preset value, after stable gas pressure drying terminates in system, are by material immersion concentration after drying Saturated concentration 70-90%, the amount of ammonium fluoride material is that the ammonium fluoride of 8-20 times of the amount of nitric acid copper material in starting aqueous solution is water-soluble Stirred 15-30 seconds in liquid and in the case where Teflon stir oar is with the speed of 1000rpm-1200rpm, filtered thereafter, in 80- Dried in 120 DEG C of drying box 3-7 hours.To be filtered after dried product exhibited immersion saturation silver nitrate solution 2-10 minute and Dried in 80-120 DEG C of drying box 3-5 hours, thereafter in the mixed gas protected lower intensification of 0.5% hydrogen and 99.5% argon gas Cooled down after constant temperature 0.5-2 hours to 450-550 DEG C, prepare continuous conduction original position C/Ag, Cu/CuF2Compound copper fluoride lithium from Sub- cell positive material.
Compared with prior art, the advantage of the invention is that：The method is by dried under low temperature, high vacuum condition Journey, copper nitrate is fixed in the Continuous Polyacrylamide body for maintaining hole and gap structure and in situ by liquid phase reactor Generation fluorination copper product, thereafter integrally changes the Continuous Polyacrylamide with hole and gap structure in heat treatment process Into the continuous carbon film with hole and gap structure, the continuous carbon film structure has high conductive capability, increases substantially multiple The electronic conductivity of condensation material；Simultaneously in heat treatment process copper fluoride particle surface reduction go out a certain amount of metallic copper and Silver, metallic copper provides homogeneity crystallization nuclei for electrode material in electric discharge, and the dynamics for reducing New phase formation hinders, and improves The capacity of material, circulation volume stability and discharge platform current potential；Silver is favorably improved exoelectrical reaction speed.It is former by reacting The immobilization of material, it is thus also avoided that the side reaction products such as various double salt of copper fluoride are generated in liquid phase reactor and there is excellent electricity Chemical property.
Brief description of the drawings
The charging capacity of preceding 10 circulations of Fig. 1 materials, discharge capacity and efficiency for charge-discharge figure, voltage range 1.8V- 4.0V, charging and discharging currents 0.1C.
Specific embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1：It is 5wt% copper nitrates, 6wt% acrylamides, 1wt%N, N to prepare composition '-methylene bisacrylamide acyl The starting aqueous solution of amine, is stirred 5 minutes using Teflon stir oar with the speed of 900rpm.By the starting aqueous solution with 5 DEG C/min speed rise to 75 DEG C and keep the temperature until starting aqueous solution turn into gelatin gel.It is solidifying by what is formed Glue is dried in the environment of low-temperature high-vacuum degree, and the drying process uses finished product freeze drier in the market, by gel It is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced to subzero 46 DEG C in sample disc, opens vavuum pump Vacuum is improved, treats that gas pressure is reduced to below 27Pa in system, opened baffle temperature control and start to dehydrate, other behaviour Machine preset value is taken as parameter, is that saturation is dense by material immersion concentration after drying after stable gas pressure drying terminates in system Degree 70%, the amount of ammonium fluoride material is in the ammonium fluoride aqueous solution of 20 times of the amount of nitric acid copper material in starting aqueous solution and poly- four PVF agitating paddle is stirred 15 seconds with 1100 speed, is filtered thereafter, is dried 3 hours in 80 DEG C of drying box.By drying Product immersion saturation silver nitrate solution is filtered after 2 minutes and dried 3 hours in 80 DEG C of drying box afterwards, thereafter in 0.5% hydrogen Gas and 99.5% argon gas it is mixed gas protected under be warmed up to 450 DEG C of constant temperature and cooled down after 0.5 hour, prepare continuous conduction former Position C/Ag, Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries.
Embodiment 2：Prepare composition 15wt% copper nitrates, 12wt% acrylamides, 2wt%N, N '-methylene bisacrylamide acyl The starting aqueous solution of amine, is stirred 14 minutes using Teflon stir oar with the speed of 1200rpm.By the starting aqueous solution with 10 DEG C/min of speed rises to 85 DEG C and keeps the temperature until starting aqueous solution is as gelatin gel.By what is formed Gel is dried in the environment of low-temperature high-vacuum degree, and the drying process, will be solidifying using finished product freeze drier in the market Glue starts refrigeration machine in being put into freeze drier sample disc, treats that gelling temp is reduced to subzero 50 DEG C in sample disc, opens vacuum Pump improves vacuum, treats that gas pressure is reduced to below 34Pa in system, opens baffle temperature control and starts to dehydrate, other Operating parameter takes machine preset value, is saturation by material immersion concentration after drying after stable gas pressure drying terminates in system Concentration 88%, the amount of ammonium fluoride material is in the ammonium fluoride aqueous solution of 8 times of the amount of nitric acid copper material in starting aqueous solution and poly- Tetrafluoroethene agitating paddle is stirred 30 seconds with the speed of 1200rpm, is filtered thereafter, is dried 7 hours in 115 DEG C of drying box. Filtered after dried product exhibited is immersed into saturation silver nitrate solution 10 minutes and dried 5 hours in 120 DEG C of drying box, existed thereafter 0.5% hydrogen and 99.5% argon gas it is mixed gas protected under be warmed up to 550 DEG C of constant temperature and cooled down after 2 hours, prepare continuous Conductive original position C/Ag, Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries.
Embodiment 3：It is 12wt% copper nitrates, 9wt% acrylamides, 1.5wt%N, N to prepare composition '-methylene bisacrylamide The starting aqueous solution of acid amides, is stirred 9 minutes using Teflon stir oar with the speed of 1100rpm.By the aqueous solution with 7 DEG C/min speed rise to 80 DEG C and keep the temperature until starting aqueous solution turn into gelatin gel.It is solidifying by what is formed Glue is dried in the environment of low-temperature high-vacuum degree, and the drying process uses finished product freeze drier in the market, by gel It is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced to subzero 48 DEG C in sample disc, opens vavuum pump Vacuum is improved, treats that gas pressure is reduced to below 30Pa in system, opened baffle temperature control and start to dehydrate, other behaviour Machine preset value is taken as parameter, is that saturation is dense by material immersion concentration after drying after stable gas pressure drying terminates in system Degree 80%, the amount of ammonium fluoride material is in the ammonium fluoride aqueous solution of 15 times of the amount of nitric acid copper material in starting aqueous solution and poly- four PVF agitating paddle is stirred 25 seconds with the speed of 1150rpm, is filtered thereafter, is dried 5 hours in 100 DEG C of drying box.Will Dried product exhibited immersion saturation silver nitrate solution is filtered after 5 minutes and dried 4 hours in 85 DEG C of drying box, is existed thereafter 0.5% hydrogen and 99.5% argon gas it is mixed gas protected under be warmed up to 500 DEG C of constant temperature and cooled down after 1 hour, prepare continuous Conductive original position C/Ag, Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries.
Embodiment 4：It is 5wt% copper nitrates, 12wt% acrylamides, 2wt%N, N to prepare composition '-methylene bisacrylamide acyl The starting aqueous solution of amine, is stirred 10 minutes using Teflon stir oar with the speed of 1000rpm.By the starting aqueous solution with 7 DEG C/min of speed rises to 80 DEG C and keeps the temperature until starting aqueous solution is as gelatin gel.It is solidifying by what is formed Glue is dried in the environment of low-temperature high-vacuum degree, and the drying process uses finished product freeze drier in the market, by gel It is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced to subzero 48 DEG C in sample disc, opens vavuum pump Vacuum is improved, treats that gas pressure is reduced to below 30Pa in system, opened baffle temperature control and start to dehydrate, other behaviour Machine preset value is taken as parameter, is that saturation is dense by material immersion concentration after drying after stable gas pressure drying terminates in system Degree 80%, the amount of ammonium fluoride material is in the ammonium fluoride aqueous solution of 10 times of the amount of nitric acid copper material in starting aqueous solution and poly- four PVF agitating paddle is stirred 22 seconds with the speed of 1150rpm, is filtered thereafter, is dried 5 hours in 110 DEG C of drying box.Will Dried product exhibited immersion saturation silver nitrate solution is filtered after 10 minutes and dried 5 hours in 90 DEG C of drying box, is existed thereafter 0.5% hydrogen and 99.5% argon gas it is mixed gas protected under be warmed up to 500 DEG C of constant temperature and cooled down after 1 hour, prepare continuous Conductive original position C/Ag, Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries.
Embodiment 5：It is 7.5wt% copper nitrates, 9wt% acrylamides, 1.5wt%N, N to prepare composition '-di-2-ethylhexylphosphine oxide third The starting aqueous solution of acrylamide, is stirred 8 minutes using Teflon stir oar with the speed of 1100rpm.By the aqueous solution with 9 DEG C/min speed rise to 81 DEG C and keep the temperature until starting aqueous solution turn into gelatin gel.It is solidifying by what is formed Glue is dried in the environment of low-temperature high-vacuum degree, and the drying process uses finished product freeze drier in the market, by gel It is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced to subzero 49 DEG C in sample disc, opens vavuum pump Vacuum is improved, treats that gas pressure is reduced to below 30Pa in system, opened baffle temperature control and start to dehydrate, other behaviour Machine preset value is taken as parameter, is that saturation is dense by material immersion concentration after drying after stable gas pressure drying terminates in system Degree 80%, the amount of ammonium fluoride material is in the ammonium fluoride aqueous solution of 16 times of the amount of nitric acid copper material in starting aqueous solution and poly- four PVF agitating paddle is stirred 25 seconds with the speed of 1120rpm, is filtered thereafter, is dried 5 hours in 100 DEG C of drying box.Will Dried product exhibited immersion saturation silver nitrate solution is filtered after 2 minutes and dried 3 hours in 100 DEG C of drying box, is existed thereafter 0.5% hydrogen and 99.5% argon gas it is mixed gas protected under be warmed up to 550 DEG C of constant temperature and cooled down after 1.5 hours, the company of preparing Continuous conduction original position C/Ag, Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries.

Claims (1)

1. a kind of continuous conduction original position C/Ag, Cu/CuF2The preparation method of compound copper fluoride anode material for lithium-ion batteries, it is special Levy for：It is 5-15wt% copper nitrates, 6-12wt% acrylamides, 1-2wt%N, N to prepare composition '-methylene-bisacrylamide The quality of starting aqueous solution, wherein acrylamide is N, 6 times of N '-methylene-bisacrylamide quality, uses polytetrafluoroethylene (PTFE) Agitating paddle is stirred 5-15 minutes with the speed of 900rpm-1200rpm；By the starting aqueous solution with 5-10 DEG C/min of speed It is raised to 75-85 DEG C and keeps the temperature until starting aqueous solution is as gelatin gel；The gel that will be formed is in existing market On finished product freeze drier on dry, gel is put into freeze drier sample disc and starts refrigeration machine, treat in sample disc coagulate Glue temperature is reduced to subzero 50 DEG C of subzero 45-, opens vavuum pump and improves vacuum, treats that gas pressure is reduced to 25- in system Below 35Pa, opens baffle temperature control and starts to dehydrate, and other operating parameters take machine preset value, treat air pressure in system It is saturated concentration 70-90% by material immersion concentration after drying after stabilization drying terminates, the amount of ammonium fluoride material is that starting is water-soluble With 1000rpm-1200rpm in the ammonium fluoride aqueous solution of 8-20 times of the amount of nitric acid copper material and in Teflon stir oar in liquid Speed under stir 15-30 seconds, filter thereafter, dried in 80-120 DEG C of drying box 3-7 hours；Dried product exhibited is immersed Saturation silver nitrate solution is filtered and dried in 80-120 DEG C of drying box 3-5 hours after 2-10 minutes, thereafter in 0.5% hydrogen With 99.5% argon gas it is mixed gas protected under be warmed up to 450-550 DEG C and cool down after constant temperature 0.5-2 hours, prepare and continuously lead Electric original position C/Ag, Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries.
CN201710213007.5A 2017-03-25 2017-03-25 A kind of continuous conduction original position C/Ag, Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries and preparation method thereof Withdrawn CN106876680A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102344151A (en) * 2011-06-23 2012-02-08 中山大学 Prussian blue nano-scale hollow olivary microballoons

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102344151A (en) * 2011-06-23 2012-02-08 中山大学 Prussian blue nano-scale hollow olivary microballoons

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
中南矿冶学院《冶金过程原理》编写小组: "《冶金过程原理》", 30 September 1973 *
张海波 等: ""聚丙烯酰胺的合成及应用研究进展"", 《高分子材料科学与工程》 *

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