CN106972157A - A kind of continuous conduction liquid phase synthesis C/Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries and preparation method thereof - Google Patents

A kind of continuous conduction liquid phase synthesis C/Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries and preparation method thereof Download PDF

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CN106972157A
CN106972157A CN201710212652.5A CN201710212652A CN106972157A CN 106972157 A CN106972157 A CN 106972157A CN 201710212652 A CN201710212652 A CN 201710212652A CN 106972157 A CN106972157 A CN 106972157A
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姘存芳
水淼
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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
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
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Abstract

A kind of continuous conduction liquid phase synthesis C/Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries and preparation method thereof, this method passes through to reaction raw materials Salzburg vitriol, the feed postition of the hybrid mode of ammonium fluoride and water, the design for adding speed, it is to avoid the side reaction products such as a variety of double salt of copper fluoride are generated in liquid phase reactor；There is the continuous carbon film of the high conductivity of hole and gap structure by the drying process under low temperature, high vacuum condition and subsequent heat treatment process formation simultaneously, the electronic conductivity of composite is increased substantially；And the surface in situ in situ in copper fluoride particle restores a certain amount of copper, homogeneity crystallization nuclei is provided in electric discharge for electrode material, the dynamics for reducing New phase formation hinders, and improves capacity, circulation volume stability and the discharge platform current potential of material.

Description

A kind of continuous conduction liquid phase synthesis C/Cu/CuF2Compound copper fluoride lithium ion cell positive Material and preparation method thereof
Technical field
The present invention relates to a kind of electric positive electrode manufacture method technical field of high-performance copper fluoride complex lithium.
Background technology
Lithium rechargeable battery has volume, weight energy higher than high, voltage, low self-discharge rate, memory-less effect, circulation Long lifespan, power density height etc. definitely advantage, had more than at present in global portable power source market 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 is brought 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 higher requirement.
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 high power consumption and high-power equipment The situation needed.But since lithium ion battery commercialization in 1991, 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 directed 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 gone 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 Circulate 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 there is larger theoretical specific capacity, it is respectively 275mAh/g and 285mAh/g, but they prepare extremely difficult, heat endurance is poor, and cyclicity is very poor, and capacity attenuation is quickly.And Progressively commercialized LiFePO4 LiFePO at present4Cost is low, heat endurance is good, environment-friendly, but its theoretical capacity About there was only 170mAh/g, and actual capacity is in 140mAh/g or so [Chun SY, Bloking J T, Chiang Y M, Nature Materials, 2002,1：123-128.].The positive electrode more than 200mAh/g specific capacities for having market prospects at present only has vanadium Sour lithium Li1+xV3O8, Li1+xV3O8Material can have possesses even close to 300mAh/g capacity, but its discharge average voltage it is relatively low and And in production process barium oxide often toxicity is larger.High lithium is than on positive electrode in recent years, particularly manganese base manganese-nickel binary and The high lithium of manganese base manganese-nickel-cobalt ternary solid solution system is steady with the Capacity Ratio more than 200mAh/g, higher heat than positive electrode The cost of qualitative and relative moderate and paid close attention to by people, but the performance under the material high magnification is very undesirable, limitation Its application [Young-Sik Hong, Yong Joon Park, et al., Solid State in electrokinetic cell Ionics, 2005,176：1035-1042].
In recent years, fluoride positive electrode is because its capacity is high, the prices of raw materials are low and enter the visual field of researcher.Fluorine The operation principle of compound material and conventional lithium ion battery positive electrode is different, 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
It 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, but often discharge curve does not have fluoride positive electrode 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 about 3.2V discharge platform voltage, 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 also has a negative characteristic to be exactly that electronic conductivity is extremely low, therefore can cause in charge and discharge process Very high polarizing voltage, 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 are kinetically being on a sticky wicket in the stage that originally forms, 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 height, technical process is environment-friendly, product quality is stable, tool The compound copper fluoride material preparation method for having excellent electrochemical performance is to be fluorinated the key that copper product is applied as secondary cell.
The content of the invention
The present invention proposes a kind of continuous conduction liquid phase synthesis C/Cu/CuF for existing background technology2Compound copper fluoride lithium Ion battery positive electrode and preparation method thereof, this method passes through the mixing side to reaction raw materials Salzburg vitriol, ammonium fluoride The feed postition of formula and water, the design for adding speed, it is to avoid it is secondary anti-to generate a variety of double salt of copper fluoride etc. in liquid phase reactor Answer product；There is hole and sky by the drying process under low temperature, high vacuum condition and subsequent heat treatment process formation simultaneously The continuous carbon film of high conductivity of gap structure, increases substantially the electronic conductivity of composite；And original position is in copper fluoride particle Surface in situ restore a certain amount of copper, for electrode material electric discharge when provide homogeneity crystallization nuclei, reduce cenotype shape Into dynamics hinder, improve capacity, circulation volume stability and the discharge platform current potential of material.
This continuous conduction liquid phase synthesis C/Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries and its preparation side Method, it is characterized in that：The amount ratio of material is put into reactor for 1: 2 Salzburg vitriol and ammonium fluoride, the reactor is not The hydrostatic column for steel matter of becoming rusty, the height of container and the ratio of diameter are 2-2.5: 1, volume of a container and Salzburg vitriol Ratio with ammonium fluoride quality sum is 2-5L/Kg, when Salzburg vitriol is less than or equal to 1Kg with ammonium fluoride quality sum, Volume of a container is 2 liters.5 circular flow entrances are set at the top of container, its center is respectively distributed to container circular top Center and mutually the angle of cut in 90 ° four radiuses midpoint, the 18-20% of its a diameter of container diameter.Salzburg vitriol and The mixture of ammonium fluoride is put into after reactor, the up-down vibration reactor, and the amplitude of vibration is 5-10 centimetres, and frequency is 1-3 times/ Second；Vibration stops vibration and sends into polyethylene glycol simultaneously from all fluid intakes of container top with identical flow velocity after 10-15 seconds Concentration is the 0.1-0.3wt% aqueous solution, flow velocity be (volume of a container/5) × 0.3- (volume of a container/5) × 0.5L/ second directly To the volume full of container 80%.Thereafter using Teflon stir oar with 900rpm-1200rpm 5-15 points of speed stirring Clock, is filtered afterwards, according to water is rejoined in the ratio solid after filtration of 100mL water/20g solids, while adding 6g third The acrylamide and 1gN, N of acrylamide/100mL waters '-methylene-bisacrylamide/100mL waters N, N '-di-2-ethylhexylphosphine oxide Acrylamide, by it with 5-10 after being stirred 5-15 minutes with 1500rpm-2000rpm speed using Teflon stir oar DEG C/min speed rise to 75-85 DEG C and keep the temperature until it becomes gelatin gel.By the gel of formation in low temperature Dried in the environment of condition of high vacuum degree, gel can be put into by the drying process using finished product freeze drier in the market 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 done in 80-120 DEG C of drying box After dry 3-7 hours 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under to be warming up to 400-480 DEG C of constant temperature 0.5-2 small When after cool down, prepare continuous conduction liquid phase synthesis C/Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries.
Compared with prior art, the advantage of the invention is that：This method passes through to reaction raw materials Salzburg vitriol, fluorination The hybrid mode of ammonium and the feed postition of water, the design for adding speed, it is to avoid a variety of of copper fluoride are generated in liquid phase reactor The side reaction products such as double salt；Have simultaneously by the drying process under low temperature, high vacuum condition and subsequent heat treatment process formation The continuous carbon film of high conductivity of hole and gap structure, increases substantially the electronic conductivity of composite；And original position exists The surface in situ of copper fluoride particle restores a certain amount of copper, provides homogeneity crystallization nuclei in electric discharge for electrode material, drops The dynamics of low New phase formation hinders, and improves capacity, circulation volume stability and the discharge platform current potential of material.
Brief description of the drawings
Charging capacity, discharge capacity and the efficiency for charge-discharge figure of preceding 10 circulations of Fig. 1 materials, voltage range 1.8V- 4.0V, charging and discharging currents 0.1C.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1：It is that Salzburg vitriol and ammonium fluoride that 1: 2 gross mass is 1Kg are put into reactor by the amount ratio of material In, the reactor is the hydrostatic column of stainless steel, and the height of container and the ratio of diameter are 2: 1, volume of a container with The ratio of Salzburg vitriol and ammonium fluoride quality sum is 2L/Kg.At the top of container, 5 circular flow entrances are set, its Center is respectively distributed to the midpoint of the center of container circular top and four radiuses of the mutual angle of cut in 90 °, and its a diameter of container is straight The 18% of footpath.The mixture of Salzburg vitriol and ammonium fluoride is put into after reactor, the up-down vibration reactor, the amplitude of vibration For 5 centimetres, frequency is 1 time/second；It is same with identical flow velocity from all fluid intakes of container top that vibration stops vibration after 10 seconds When feeding Polyethylene glycol be 0.1wt% the aqueous solution, flow velocity be (volume of a container/5) × 0.3L/ seconds until full of container 80% volume.Thereafter stirred 5 minutes, filtered afterwards, according to 100mL with 900rpm speed using Teflon stir oar Water is rejoined in the solid of the ratio of water/20g solids after filtration, while adding the propylene of 6g acrylamides/100mL waters Acid amides and 1gN, N '-methylene-bisacrylamide/100mL waters N, N '-methylene-bisacrylamide, use polytetrafluoroethylene (PTFE) It is risen to 75 DEG C with 5 DEG C/min of speed after being stirred 5 minutes with 1500rpm speed and keeps the temperature straight by agitating paddle To as gelatin gel.The gel of formation is dried in the environment of low-temperature high-vacuum degree, the drying process is using current The finished product freeze drier of in the market, gel is put into freeze drier sample disc and starts refrigeration machine, treats gel in sample disc Temperature is reduced to subzero 45 DEG C, opens vavuum pump and improves vacuum, treats that gas pressure is reduced to below 25Pa in system, open every Plate temperature control starts to dehydrate, and other operating parameters take machine preset value, after stable gas pressure drying terminates in system, After being dried 3 hours in 80 DEG C of drying box 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 400 DEG C Constant temperature is cooled down after 0.5 hour, prepares continuous conduction liquid phase synthesis C/Cu/CuF2Compound copper fluoride lithium ion cell positive material Material.
Embodiment 2：It is that Salzburg vitriol and ammonium fluoride that 1: 2 gross mass is 2Kg are put into reactor by the amount ratio of material In, the reactor is the hydrostatic column of stainless steel, and the height of container and the ratio of diameter are 2.2: 1, volume of a container Ratio with Salzburg vitriol and ammonium fluoride quality sum is 3L/Kg.At the top of container, 5 circular flow entrances are set, Its center is respectively distributed to the midpoint of the center of container circular top and four radiuses of the mutual angle of cut in 90 °, its a diameter of container The 19% of diameter.The mixture of Salzburg vitriol and ammonium fluoride is put into after reactor, the up-down vibration reactor, the width of vibration Spend for 7 centimetres, frequency is 2 times/second；Vibration stops vibration from all fluid intakes of container top with identical flow velocity after 12 seconds The aqueous solution that Polyethylene glycol is 0.2wt% is sent into simultaneously, and flow velocity is (volume of a container/5) × 0.5L/ seconds until full of appearance The volume of device 80%.Thereafter stirred 10 minutes, filtered afterwards with 1100rpm speed using Teflon stir oar, according to Water is rejoined in the solid of the ratio of 100mL water/20g solids after filtration, while adding 6g acrylamides/100mL waters Acrylamide and 1gN, N '-methylene-bisacrylamide/100mL waters N, N '-methylene-bisacrylamide, use poly- four It is risen to 85 DEG C with 10 DEG C/min of speed after being stirred 12 minutes with 2000rpm speed and kept by PVF agitating paddle The temperature is until it becomes gelatin gel.The gel of formation is dried in the environment of low-temperature high-vacuum degree, the drying process Using finished product freeze drier in the market, gel is put into freeze drier sample disc and starts refrigeration machine, sample is treated Gelling temp is reduced to subzero 50 DEG C on disk, opens vavuum pump and improves vacuum, treat in system gas pressure be reduced to 33Pa with Under, open baffle temperature control and start to dehydrate, other operating parameters take machine preset value, treat that stable gas pressure is done in system After constipation beam, after being dried 5 hours in 100 DEG C of drying box 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under It is warming up to 440 DEG C of constant temperature to cool down after 1 hour, prepares continuous conduction liquid phase synthesis C/Cu/CuF2Compound copper fluoride lithium ion Cell positive material.
Embodiment 3：It is that Salzburg vitriol and ammonium fluoride that 1: 2 gross mass is 3Kg are put into reactor by the amount ratio of material In, the reactor is the hydrostatic column of stainless steel, and the height of container and the ratio of diameter are 2.5: 1, volume of a container Ratio with Salzburg vitriol and ammonium fluoride quality sum is 5L/Kg.At the top of container, 5 circular flow entrances are set, Its center is respectively distributed to the midpoint of the center of container circular top and four radiuses of the mutual angle of cut in 90 °, its a diameter of container The 20% of diameter.The mixture of Salzburg vitriol and ammonium fluoride is put into after reactor, the up-down vibration reactor, the width of vibration Spend for 10 centimetres, frequency is 3 times/second；Vibration stops vibration from all fluid intakes of container top with identical stream after 15 seconds Speed simultaneously send into Polyethylene glycol be 0.3wt% the aqueous solution, flow velocity be (volume of a container/5) × 0.4L/ seconds until full of The volume of container 80%.Thereafter stirred 15 minutes with 1200rpm speed using Teflon stir oar, filter, press afterwards According to water is rejoined in the ratio solid after filtration of 100mL water/20g solids, while adding 6g acrylamides/100mL water The acrylamide and 1gN, N of amount '-methylene-bisacrylamide/100mL waters N, N '-methylene-bisacrylamide, using poly- It is risen to 80 DEG C with 8 DEG C/min of speed after being stirred 10 minutes with 1800pm speed and kept by tetrafluoroethene agitating paddle The temperature is until it becomes gelatin gel.The gel of formation is dried in the environment of low-temperature high-vacuum degree, the drying process Using finished product freeze drier in the market, gel is put into freeze drier sample disc and starts refrigeration machine, sample is treated Gelling temp is reduced to subzero 48 DEG C on disk, opens vavuum pump and improves vacuum, treat in system gas pressure be reduced to 30Pa with Under, open baffle temperature control and start to dehydrate, other operating parameters take machine preset value, treat that stable gas pressure is done in system After constipation beam, after being dried 7 hours in 120 DEG C of drying box 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under It is warming up to 480 DEG C of constant temperature to cool down after 2 hours, prepares continuous conduction liquid phase synthesis C/Cu/CuF2Compound copper fluoride lithium ion Cell positive material.
Embodiment 4：It is that Salzburg vitriol and ammonium fluoride that 1: 2 gross mass is 1Kg are put into reactor by the amount ratio of material In, the reactor is the hydrostatic column of stainless steel, and the height of container and the ratio of diameter are 2: 1, volume of a container with The ratio of Salzburg vitriol and ammonium fluoride quality sum is 2.5L/Kg.At the top of container, 5 circular flow entrances are set, Its center is respectively distributed to the midpoint of the center of container circular top and four radiuses of the mutual angle of cut in 90 °, its a diameter of container The 18% of diameter.The mixture of Salzburg vitriol and ammonium fluoride is put into after reactor, the up-down vibration reactor, the width of vibration Spend for 5 centimetres, frequency is 1 time/second；Vibration stops vibration from all fluid intakes of container top with identical flow velocity after 10 seconds The aqueous solution that Polyethylene glycol is 0.1wt% is sent into simultaneously, and flow velocity is (volume of a container/5) × 0.4L/ seconds until full of appearance The volume of device 80%.Thereafter stirred 10 minutes, filtered afterwards with 1150rpm speed using Teflon stir oar, according to Water is rejoined in the solid of the ratio of 100mL water/20g solids after filtration, while adding 6g acrylamides/100mL waters Acrylamide and 1gN, N '-methylene-bisacrylamide/100mL waters N, N '-methylene-bisacrylamide, use poly- four It is risen to 85 DEG C with 10 DEG C/min of speed after being stirred 5 minutes with 1500rpm speed and keeps being somebody's turn to do by PVF agitating paddle Temperature is until it becomes gelatin gel.The gel of formation is dried in the environment of low-temperature high-vacuum degree, the drying process is adopted With finished product freeze drier in the market, gel is put into freeze drier sample disc and starts refrigeration machine, sample disc is treated Upper gelling temp is reduced to subzero 45 DEG C, opens vavuum pump and improves vacuum, treats that gas pressure is reduced to below 28Pa in system, Open baffle temperature control to start to dehydrate, other operating parameters take machine preset value, treat that stable gas pressure is dried in system After end, in 0.1% hydrogen and the mixed gas protected lower liter of 99.9% argon gas after being dried 5 hours in 110 DEG C of drying box Warm to 420 DEG C constant temperature are cooled down after 1 hour, prepare continuous conduction liquid phase synthesis C/Cu/CuF2Compound copper fluoride lithium-ion electric Pond positive electrode.
Embodiment 5：It is that Salzburg vitriol and ammonium fluoride that 1: 2 gross mass is 2Kg are put into reactor by the amount ratio of material In, the reactor is the hydrostatic column of stainless steel, and the height of container and the ratio of diameter are 2.2: 1, volume of a container Ratio with Salzburg vitriol and ammonium fluoride quality sum is 3L/Kg.At the top of container, 5 circular flow entrances are set, Its center is respectively distributed to the midpoint of the center of container circular top and four radiuses of the mutual angle of cut in 90 °, its a diameter of container The 20% of diameter.The mixture of Salzburg vitriol and ammonium fluoride is put into after reactor, the up-down vibration reactor, the width of vibration Spend for 10 centimetres, frequency is 3 times/second；Vibration stops vibration from all fluid intakes of container top with identical stream after 15 seconds Speed simultaneously send into Polyethylene glycol be 0.2wt% the aqueous solution, flow velocity be (volume of a container/5) × 0.3L/ seconds until full of The volume of container 80%.Thereafter stirred 15 minutes with 1200rpm speed using Teflon stir oar, filter, press afterwards According to water is rejoined in the ratio solid after filtration of 100mL water/20g solids, while adding 6g acrylamides/100mL water The acrylamide and 1gN, N of amount '-methylene-bisacrylamide/100mL waters N, N '-methylene-bisacrylamide, using poly- It is risen to 82 DEG C with 6 DEG C/min of speed after being stirred 12 minutes with 2000rpm speed and kept by tetrafluoroethene agitating paddle The temperature is until it becomes gelatin gel.The gel of formation is dried in the environment of low-temperature high-vacuum degree, the drying process Using finished product freeze drier in the market, gel is put into freeze drier sample disc and starts refrigeration machine, sample is treated Gelling temp is reduced to subzero 47 DEG C on disk, opens vavuum pump and improves vacuum, treat in system gas pressure be reduced to 28Pa with Under, open baffle temperature control and start to dehydrate, other operating parameters take machine preset value, treat that stable gas pressure is done in system After constipation beam, after being dried 5 hours in 120 DEG C of drying box 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under It is warming up to 460 DEG C of constant temperature to cool down after 1.5 hours, prepares continuous conduction liquid phase synthesis C/Cu/CuF2Compound copper fluoride lithium from Sub- cell positive material.

Claims (1)

1. a kind of continuous conduction liquid phase synthesis C/Cu/CuF2The preparation method of compound copper fluoride anode material for lithium-ion batteries, it is special Levy for：The amount ratio of material is put into reactor for 1: 2 Salzburg vitriol and ammonium fluoride, the reactor is stainless steel Hydrostatic column, the height of container and the ratio of diameter are 2-2.5: 1, volume of a container and Salzburg vitriol and ammonium fluoride The ratio of quality sum is 2-5L/Kg, when Salzburg vitriol is less than or equal to 1Kg with ammonium fluoride quality sum, the body of container Product is 2 liters；Container top set 5 circular flow entrances, its center be respectively distributed to container circular top center and The midpoint of four radiuses of the mutual angle of cut in 90 °, the 18-20% of its a diameter of container diameter；Salzburg vitriol and ammonium fluoride Mixture is put into after reactor, the up-down vibration reactor, and the amplitude of vibration is 5-10 centimetres, and frequency is 1-3 times/second；Vibration After 10-15 seconds stop vibration from all fluid intakes of container top using identical flow velocity simultaneously send into Polyethylene glycol as The 0.1-0.3wt% aqueous solution, flow velocity be (volume of a container/5) × 0.3- (volume of a container/5) × 0.5L/ seconds until full of The volume of container 80%；Thereafter stirred 5-15 minutes with 900rpm-1200rpm speed using Teflon stir oar, it After filter, according to water is rejoined in the ratio solid after filtration of 100mL water/20g solids, while adding 6g acryloyls The acrylamide and 1gN, N of amine/100mL waters '-methylene-bisacrylamide/100mL waters N, N '-methylene bisacrylamide Acid amides, by it with 5-10 DEG C/minute after being stirred 5-15 minutes with 1500rpm-2000rpm speed using Teflon stir oar The speed of clock rises to 75-85 DEG C and keeps the temperature until it becomes gelatin gel；By the gel of formation 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, other operating parameters take machine preset value, treat air pressure in system Stablize after dry terminate, in the mixing of 0.1% hydrogen and 99.9% argon gas after being dried 3-7 hours in 80-120 DEG C of drying box 400-480 DEG C of constant temperature is warming up under gas shield to cool down after 0.5-2 hours, prepares continuous conduction liquid phase synthesis C/Cu/ CuF2Compound copper fluoride anode material for lithium-ion batteries.
CN201710212652.5A 2017-03-25 2017-03-25 A kind of continuous conduction liquid phase synthesis C/Cu/CuF2Compound copper fluoride anode material for lithium-ion batteries and preparation method thereof Withdrawn CN106972157A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108767236A (en) * 2018-06-02 2018-11-06 湖南科技大学 A kind of preparation method of lithium ion battery Cu/LiF composite positive poles

Non-Patent Citations (1)

* 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 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108767236A (en) * 2018-06-02 2018-11-06 湖南科技大学 A kind of preparation method of lithium ion battery Cu/LiF composite positive poles
CN108767236B (en) * 2018-06-02 2021-01-08 湖南科技大学 Preparation method of Cu/LiF composite anode material of lithium ion battery

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