CN106876679A - A kind of non-acid system liquid phase synthesis continuous conduction C/Zr/ZrF4Compound zirconium fluoride anode material for lithium-ion batteries and preparation method thereof - Google Patents
A kind of non-acid system liquid phase synthesis continuous conduction C/Zr/ZrF4Compound zirconium fluoride anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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Abstract
A kind of non-acid system liquid phase synthesis continuous conduction C/Zr/ZrF4Compound zirconium fluoride anode material for lithium-ion batteries and preparation method thereof, the method is by the feed postition to the nitric hydrate zirconium of reaction raw materials five, the hybrid mode of ammonium fluoride and water, the design of addition speed, eliminate the addition of the dust technology for suppressing hydrolysis, it is to avoid dust technology has the risk that high toxicity hydrogen fluoride is produced with ammonium fluoride effect；Being formed by the drying process and subsequent heat treatment process under low temperature, high vacuum condition simultaneously has the continuous carbon film of the high conductivity of hole and gap structure, and original position restores a certain amount of zirconium in the surface in situ of zirconium fluoride particle, for electrode material provides homogeneity crystallization nuclei in electric discharge, the dynamics for reducing New phase formation hinders；Also avoid and the side reaction products such as various double salt of zirconium fluoride are generated in liquid phase reactor and with excellent chemical property.
Description
Technical field
The present invention relates to a kind of high-performance zirconium 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 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 possess even close to 300mAh/g capacity, but its electric discharge average voltage it is relatively low and
And in production process barium oxide often toxicity is larger.Lithium high is than on positive electrode in recent years, particularly manganese base manganese-nickel binary and
The lithium high of manganese base manganese-nickel-cobalt ternary solid solution system is steady with the Capacity Ratio more than 200mAh/g, heat higher 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 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.Wherein zirconium fluoride has big advantage due to there is specific discharge capacity very high.The conjunction of conventional zirconium fluoride
Into method to be reacted with metal simple-substance with metal oxide/hydroxide or fluorine gas with hydrogen fluoride gas at high temperature, work
Skill condition is harsh, and equipment requirement is very high, high energy consumption, therefore price is very expensive.And liquid phase reactor prepares zirconium fluoride then often
Because by-products content is too high cannot be used as positive electrode simultaneously because hydrolyzed in water and added to suppress zirconium nitrate
Dust technology exist with ammonium fluoride effect produce high toxicity hydrogen fluoride risk.Zirconium fluoride is used as lithium ion secondary battery positive electrode
It is extremely low its electronic conductivity that material also has a negative characteristic, therefore can cause polarization very high in charge and discharge process
Voltage.Although having researcher improves the electrical conductivity of material using carbon black mixing and ball milling is added, but granular carbon black
It is difficult to form complete electrically conductive links, increases substantially its electronic conductivity.Finally, the material electric discharge when produce metal zirconium and
Lithium fluoride cenotype, cenotype small particles in the stage that originally forms being kinetically on a sticky wicket, therefore to discharge and recharge thereafter
Capacity, 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 zirconium fluoride material preparation method for having excellent electrochemical performance is the key for being fluorinated zirconia material as secondary cell application.
The content of the invention
The present invention proposes a kind of non-acid system liquid phase synthesis continuous conduction C/Zr/ZrF for existing background technology4It is compound
Zirconium fluoride anode material for lithium-ion batteries and preparation method thereof, the method is by the nitric hydrate zirconium of reaction raw materials five, ammonium fluoride
Hybrid mode and water feed postition, add the design of speed, eliminate the addition of the dust technology for suppressing hydrolysis, it is to avoid dilute
Nitric acid has the risk that high toxicity hydrogen fluoride is produced with ammonium fluoride effect；Simultaneously by the drying under low temperature, high vacuum condition
Process and subsequent heat treatment process are formed has the continuous carbon film of the high conductivity of hole and gap structure, increases substantially compound
The electronic conductivity of material；It is that electrode material exists and original position restores a certain amount of zirconium in the surface in situ of zirconium fluoride particle
Homogeneity crystallization nuclei is provided during electric discharge, the dynamics for reducing New phase formation hinders, and improves capacity, the circulation volume of material
Stability and discharge platform current potential；Such reaction mechanism mechanism of reaction also avoid and various double salt of zirconium fluoride etc. are generated in liquid phase reactor
Side reaction product simultaneously has excellent chemical property.
This non-acid system liquid phase synthesis continuous conduction C/Zr/ZrF4Compound zirconium fluoride anode material for lithium-ion batteries and its
Preparation method, it is characterized by：By the amount ratio of material for 1: 4 five nitric hydrate zirconiums and ammonium fluoride are put into reactor, the reaction
Device is the hydrostatic column of stainless steel, and the height of container and the ratio of diameter are 2-2.5: 1, and volume of a container and five is hydrated
The ratio of zirconium nitrate and ammonium fluoride quality sum is 2-5L/Kg, when five nitric hydrate zirconiums and ammonium fluoride quality sum are less than or equal to
During 1Kg, 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 circle
Four midpoints of radius at center and the mutual angle of cut in 90 ° at the top of shape, the 18-20% of its a diameter of container diameter.Five hydration nitre
After the mixture of sour zirconium and ammonium fluoride is put into reactor, the up-down vibration reactor, the amplitude of vibration is 5-10 centimetres, and frequency is
1-3 times/second；Vibration stops vibration after 10-15 seconds from all fluid intakes of container top, with identical flow velocity, feeding is poly- simultaneously
Glycol concentration for 0.1-0.3wt% the aqueous solution, flow velocity be (volume of a container/5) × 0.3- (volume of a container/5) ×
0.5L/ seconds until the volume full of container 80%.Thereafter using Teflon stir oar with the speed of 900rpm-1200rpm
Stirring 5-15 minutes, filters afterwards, according to water is rejoined in the ratio solid after filtration of 100mL water/20g solids, together
When add the acrylamide and 1gN, N of 6g acrylamides/100mL waters ' N of-methylene-bisacrylamide/100mL waters,
N '-methylene-bisacrylamide, after being stirred 5-15 minutes with the speed of 1500rpm-2000rpm using Teflon stir oar
It with 5-10 DEG C/min of speed is risen to 75-85 DEG C and the temperature is kept until it becomes gelatin gel.By what is formed
Gel is dried in the environment of low-temperature high-vacuum degree, and the drying process can use finished product freeze drier in the market,
Gel is put into freeze drier sample disc and starts refrigeration machine, treat that gelling temp is reduced to subzero 45- subzero 50 in sample disc
DEG C, open vavuum pump and improve vacuum, treat that gas pressure is reduced to below 25-35Pa in system, open baffle temperature control and open
Beginning dehydrates, and other operating parameters take machine preset value, after stable gas pressure drying terminates in system, at 80-120 DEG C
After being dried in drying box 3-7 hours 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warmed up to 400-480 DEG C of perseverance
Cooled down after warm 0.5-2 hours, prepare non-acid system liquid phase synthesis continuous conduction C/Zr/ZrF4Compound zirconium fluoride lithium-ion electric
Pond positive electrode.
Compared with prior art, the advantage of the invention is that：The method is by the nitric hydrate zirconium of reaction raw materials five, fluorination
The hybrid mode of ammonium and the feed postition of water, the design for adding speed, eliminate the addition of the dust technology for suppressing hydrolysis, it is to avoid
Dust technology has the risk that high toxicity hydrogen fluoride is produced with ammonium fluoride effect；Simultaneously by dry under low temperature, high vacuum condition
Dry process and subsequent heat treatment process are formed has the continuous carbon film of the high conductivity of hole and gap structure, increases substantially multiple
The electronic conductivity of condensation material；It is electrode material and original position restores a certain amount of zirconium in the surface in situ of zirconium fluoride particle
Homogeneity crystallization nuclei is provided in electric discharge, the dynamics for reducing New phase formation hinders, improve the capacity of material, circulation and hold
Amount stability and discharge platform current potential；Such reaction mechanism mechanism of reaction also avoid various double salt that zirconium fluoride is generated in liquid phase reactor
Deng side reaction product and with excellent 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 that five nitric hydrate zirconiums and ammonium fluoride that 1: 4 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 and
The ratio of five nitric hydrate zirconiums 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 center of container circular top and four midpoints of radius of the mutual angle of cut in 90 °, and its a diameter of container is straight
The 18% of footpath.After the mixture of five nitric hydrate zirconiums and ammonium fluoride is put into reactor, the up-down vibration reactor, the amplitude of vibration
It it is 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 for 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 with the speed of 900rpm using Teflon stir oar, filtered afterwards, according to 100mL
Water is rejoined in the ratio of water/20g solids solid 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 with 5 DEG C/min of speed is risen to 75 DEG C and keeps the temperature straight by agitating paddle after being stirred 5 minutes with the speed of 1500rpm
To as gelatin gel.The gel that will be formed is dried in the environment of low-temperature high-vacuum degree, and 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 drying 3 hours in 80 DEG C of the drying box 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warmed up to 400 DEG C
Constant temperature is cooled down after 0.5 hour, prepares non-acid system liquid phase synthesis continuous conduction C/Zr/ZrF4Compound zirconium fluoride lithium-ion electric
Pond positive electrode.
Embodiment 2：It is that five nitric hydrate zirconiums and ammonium fluoride that 1: 4 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
It is 3L/Kg with the ratio of five nitric hydrate zirconiums and ammonium fluoride quality sum.At the top of container, 5 circular flow entrances are set,
Its center is respectively distributed to the center of container circular top and four midpoints of radius of the mutual angle of cut in 90 °, its a diameter of container
The 19% of diameter.After the mixture of five nitric hydrate zirconiums and ammonium fluoride is put into reactor, the up-down vibration reactor, the width of vibration
It is 7 centimetres to spend, and frequency is 2 times/second；Vibration stops vibration from all fluid intakes of container top with identical flow velocity after 12 seconds
It is the aqueous solution of 0.2wt% to send into Polyethylene glycol 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 with the speed of 1100rpm using Teflon stir oar, filtered afterwards, according to
Water is rejoined in the ratio of 100mL water/20g solids solid after filtration, while adding 6g acrylamides/100mL waters
Acrylamide and 1gN, N '-methylene-bisacrylamide/100mL waters N, N '-methylene-bisacrylamide, use poly- four
It with 10 DEG C/min of speed is risen to 85 DEG C and kept by PVF agitating paddle after being stirred 12 minutes with the speed of 2000rpm
The temperature is until it becomes gelatin gel.The gel that will be formed 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, treat sample
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, to 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 drying 5 hours in 100 DEG C of the drying box 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under
It is warmed up to 440 DEG C of constant temperature to be cooled down after 1 hour, prepares non-acid system liquid phase synthesis continuous conduction C/Zr/ZrF4Compound fluorination
Zirconium anode material for lithium-ion batteries.
Embodiment 3：It is that five nitric hydrate zirconiums and ammonium fluoride that 1: 4 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
It is 5L/Kg with the ratio of five nitric hydrate zirconiums and ammonium fluoride quality sum.At the top of container, 5 circular flow entrances are set,
Its center is respectively distributed to the center of container circular top and four midpoints of radius of the mutual angle of cut in 90 °, its a diameter of container
The 20% of diameter.After the mixture of five nitric hydrate zirconiums and ammonium fluoride is put into reactor, the up-down vibration reactor, the width of vibration
It is 10 centimetres to spend, and frequency is 3 times/second；Vibration stops vibration from all fluid intakes of container top with identical stream after 15 seconds
It is the aqueous solution of 0.3wt% that speed sends into Polyethylene glycol simultaneously, and flow velocity is (volume of a container/5) × 0.4L/ seconds until being full of
The volume of container 80%.Thereafter stirred 15 minutes with the speed of 1200rpm using Teflon stir oar, filtered afterwards, pressed
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 with 8 DEG C/min of speed is risen to 80 DEG C and kept by tetrafluoroethene agitating paddle after being stirred 10 minutes with the speed of 1800pm
The temperature is until it becomes gelatin gel.The gel that will be formed 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, treat sample
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, to 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 drying 7 hours in 120 DEG C of the drying box 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under
It is warmed up to 480 DEG C of constant temperature to be cooled down after 2 hours, prepares non-acid system liquid phase synthesis continuous conduction C/Zr/ZrF4Compound fluorination
Zirconium anode material for lithium-ion batteries.
Embodiment 4：It is that five nitric hydrate zirconiums and ammonium fluoride that 1: 4 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 and
The ratio of five nitric hydrate zirconiums 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 center of container circular top and four midpoints of radius of the mutual angle of cut in 90 °, its a diameter of container
The 18% of diameter.After the mixture of five nitric hydrate zirconiums and ammonium fluoride is put into reactor, the up-down vibration reactor, the width of vibration
It is 5 centimetres to spend, and frequency is 1 time/second；Vibration stops vibration from all fluid intakes of container top with identical flow velocity after 10 seconds
It is the aqueous solution of 0.1wt% to send into Polyethylene glycol 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 with the speed of 1150rpm using Teflon stir oar, filtered afterwards, according to
Water is rejoined in the ratio of 100mL water/20g solids solid after filtration, while adding 6g acrylamides/100mL waters
Acrylamide and 1gN, N '-methylene-bisacrylamide/100mL waters N, N '-methylene-bisacrylamide, use poly- four
It with 10 DEG C/min of speed is risen to 85 DEG C and keeps this by PVF agitating paddle after being stirred 5 minutes with the speed of 1500rpm
Temperature is until it becomes gelatin gel.The gel that will be formed is dried in the environment of low-temperature high-vacuum degree, and 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, treat sample disc
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 non-acid system liquid phase synthesis continuous conduction C/Zr/ZrF4Compound zirconium fluoride
Anode material for lithium-ion batteries.
Embodiment 5：It is that five nitric hydrate zirconiums and ammonium fluoride that 1: 4 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
It is 3L/Kg with the ratio of five nitric hydrate zirconiums and ammonium fluoride quality sum.At the top of container, 5 circular flow entrances are set,
Its center is respectively distributed to the center of container circular top and four midpoints of radius of the mutual angle of cut in 90 °, its a diameter of container
The 20% of diameter.After the mixture of five nitric hydrate zirconiums and ammonium fluoride is put into reactor, the up-down vibration reactor, the width of vibration
It is 10 centimetres to spend, and frequency is 3 times/second；Vibration stops vibration from all fluid intakes of container top with identical stream after 15 seconds
It is the aqueous solution of 0.2wt% that speed sends into Polyethylene glycol simultaneously, and flow velocity is (volume of a container/5) × 0.35L/ seconds until filling
The volume of full container 80%.Thereafter stirred 15 minutes with the speed of 1200rpm using Teflon stir oar, filtered afterwards,
According to water is rejoined in the ratio solid after filtration of 100mL water/20g solids, while adding 6g acrylamides/100mL
The acrylamide and 1gN, N of water '-methylene-bisacrylamide/100mL waters N, N '-methylene-bisacrylamide, use
It with 6 DEG C/min of speed is risen to 82 DEG C and protected by Teflon stir oar after being stirred 12 minutes with the speed of 2000rpm
The temperature is held until it becomes gelatin gel.The gel that will be formed is dried in the environment of low-temperature high-vacuum degree, and this is dried
Cheng Caiyong finished product freeze driers in the market, gel are put into freeze drier sample disc and start refrigeration machine, treat sample
Gelling temp is reduced to subzero 47 DEG C on product disk, opens vavuum pump and improves vacuum, treats that gas pressure is reduced to 28Pa in system
Hereinafter, open baffle temperature control to start to dehydrate, other operating parameters take machine preset value, treat stable gas pressure in system
It is mixed gas protected with 99.9% argon gas in 0.1% hydrogen after being dried 5 hours in 120 DEG C of drying box after drying terminates
Under be warmed up to 460 DEG C of constant temperature and cooled down after 1.5 hours, prepare non-acid system liquid phase synthesis continuous conduction C/Zr/ZrF4It is compound
Zirconium fluoride anode material for lithium-ion batteries.
Claims (1)
1. a kind of non-acid system liquid phase synthesis continuous conduction C/Zr/ZrF4The preparation of compound zirconium fluoride anode material for lithium-ion batteries
Method, it is characterized by：By the amount ratio of material for 1: 4 five nitric hydrate zirconiums and ammonium fluoride are put into reactor, the reactor is
The hydrostatic column of stainless steel, the height of container and the ratio of diameter are 2-2.5: 1, volume of a container and five nitric hydrates
The ratio of zirconium and ammonium fluoride quality sum is 2-5L/Kg, when five nitric hydrate zirconiums and ammonium fluoride quality sum are less than or equal to 1Kg
When, 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
The center in portion and mutually four midpoints of radius of the angle of cut in 90 °, the 18-20% of its a diameter of container diameter；Five nitric hydrate zirconiums
After reactor being put into the mixture of ammonium fluoride, the up-down vibration reactor, the amplitude of vibration is 5-10 centimetres, and frequency is 1-3
Secondary/second；Vibration stops vibration and sends into poly- second two simultaneously with identical flow velocity from all fluid intakes of container top after 10-15 seconds
Determining alcohol is the aqueous solution of 0.1-0.3wt%, and flow velocity is (volume of a container/5) × 0.3- (volume of a container/5) × 0.5L/ seconds
Until the volume full of container 80%；Thereafter 5-15 is stirred with the speed of 900rpm-1200rpm using Teflon stir oar
Minute, filter afterwards, according to water is rejoined in the ratio solid after filtration of 100mL water/20g solids, while adding 6g
The acrylamide and 1gN, N of acrylamide/100mL waters '-methylene-bisacrylamide/100mL waters N, N '-methylene
Bisacrylamide, by it with 5- after being stirred 5-15 minutes with the speed of 1500rpm-2000rpm using Teflon stir oar
10 DEG C/min of speed rises to 75-85 DEG C and keeps the temperature until it becomes gelatin gel；The gel that will be formed is in mesh
Dried on the finished product freeze drier of preceding in the market, gel is put into freeze drier sample disc and starts refrigeration machine, treat sample
Gelling temp is reduced to subzero 50 DEG C of subzero 45- on disk, opens vavuum pump and improves vacuum, treats that gas pressure is reduced in system
Below 25-35Pa, opens baffle temperature control and starts to dehydrate, and other operating parameters take machine preset value, treat in system
Stable gas pressure is dried after terminating, in 0.1% hydrogen and 99.9% argon gas after being dried in 80-120 DEG C of drying box 3-7 hours
400-480 DEG C is warmed up under mixed gas protected to cool down after constant temperature 0.5-2 hours, prepares non-acid system liquid phase synthesis continuous
Conductive C/Zr/ZrF4Compound zirconium fluoride anode material for lithium-ion batteries.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496722A (en) * | 2011-12-22 | 2012-06-13 | 南开大学 | Layered lithium-rich anode material clad by metal fluoride, and preparation method thereof |
| CN104183842A (en) * | 2014-08-14 | 2014-12-03 | 东莞新能源科技有限公司 | Anode material and preparation method thereof |
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2017
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496722A (en) * | 2011-12-22 | 2012-06-13 | 南开大学 | Layered lithium-rich anode material clad by metal fluoride, and preparation method thereof |
| CN104183842A (en) * | 2014-08-14 | 2014-12-03 | 东莞新能源科技有限公司 | Anode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHANG, XP 等: ""Multifunctional ZrF4 nanocoating for improving lithium storage performances in layered Li[Li0.2Ni0.17Co0.07Mn0.56]O2"", 《SOLID STATE IONICS》 * |
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