CN107093743B - The preparation method of water system power battery combined conductive agent - Google Patents
The preparation method of water system power battery combined conductive agent Download PDFInfo
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- CN107093743B CN107093743B CN201710405272.3A CN201710405272A CN107093743B CN 107093743 B CN107093743 B CN 107093743B CN 201710405272 A CN201710405272 A CN 201710405272A CN 107093743 B CN107093743 B CN 107093743B
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- 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
The invention belongs to function powder material preparation technical fields, and in particular to a kind of preparation method of water system power battery combined conductive agent.Sodium oxalate water solution and nickel sulfate solution are add to deionized water simultaneously and reacted, reaction generates amorphous precipitated nickel oxalate；Aged, separation of solid and liquid obtains filter cake；Filter cake is added in HPMC glue and is stirred into slurry；Slurry is spray-dried at spheric granules；Spheric granules is using hydrogen reduction up to spherical ultra-fine nickel powder/carbon material.The present invention prepares spherical ultra-fine nickel powder/carbon material of the granularity at 0.06-1.2 μm under no adjuvant, the requirement of water system power battery combined conductive agent is fully met, oxygen content is low, and properties of product are stablized, favorable reproducibility, and production process is nontoxic, pollution-free, environmental-friendly, excellent product performance, meets the needs of water system power battery combined conductive agent, alternative foreign countries' imported product, breaks foreign technology monopolization, makes up domestic technique blank.
Description
Technical field
The invention belongs to function powder material preparation technical fields, and in particular to a kind of water system power battery composite conducting
The preparation method of agent.
Background technique
Extra-fine nickel powder is widely applied always in water system power battery as conductive agent as excellent conductive agent.Mesh
Preceding extra-fine nickel powder production technology mainly includes carbonyl process, electrolysis method, atomization, gas phase reduction process, normal pressure liquid phase reduction, consolidates
Phase reduction method, gamma Rays method, wherein the most commonly used with carbonyl process.Carbonyl process makes under 573~673K that is, in decomposer
Ni(CO)4It decomposes, by adjusting technological parameter, controls forming core, growth, reunion and the sintering behavior of metal nickel powder, prepare " chain
The extra-fine nickel powder of pearl " shape pattern in further processing, is easily formed tridimensional network, adds especially suitable for electrodes conduct
The fields such as agent.This method is broadly divided into the progress of two steps, and CO and nickel reactant is made to generate carbonyl nickel Ni (CO) first4, then in heat point
Carbonyl nickel is set to decompose to obtain nickel powder in solution furnace.The obtained nickel powder granularity of different thermal decomposition furnaces and pattern difference, such as wall heating type
The nickel powder that the nickel powder of pyrolysis oven production shows spherical, pre-heated pyrolysis oven production shows the nickel powder of near-spherical, the production of Recuperative heat type pyrolysis oven
In chain pearl；Gained nickel powder granularity generally at 1 μm or more, there is preferable application performance, especially suitable for electrodes conduct additive
Equal fields.The carbonyl process that the northern nickel company (Norisk) of International Nickel company of Canada Ltd. (INCO) and Russia possesses nickel extracts and adds
Work technology, occupy rank first, and carbonyl process production technology has at low cost, and product purity is high, pattern and granularity are easy to adjust
The advantages that section, but carbonyl nickel category extremely toxic substance, equipment requirement is high, control difficulty is big, and carbonyl process produces nickel powder technology always in addition
For Canadian INCO company monopolizing, the country is also only at the laboratory research stage, and the country is at development phase or only
There can be feather weight sample, large-scale production can not be formed, China fails to grasp comprehensively always, and domestic tonne or more of user is main
Also it is to rely on imported product.
Electrolysis method makees electrolyte with nickel chloride or nickel sulfate, and using electrolytic nickel as anode, graphite or stainless steel make cathode, one
Electrolytically generated electrolytic nickel powder under fixed condition, gained nickel powder since oxygen content is higher, need 500 DEG C or so with after hydrogen reducing
It can use.Atomization is that metallic nickel is melt into liquid, is crushed molten metal in spray chamber with high-speed flow and is atomized into
Fine droplet, finally rapidly by Drop Condensation at solid powder, atomized nickel powder.Its core is control gas to metal liquid stream
Effect, nozzle design be gas atomization key technology.Electrolysis method, the nickel powder Fisher particle size of atomization preparation are generally in 1.0 μ
M or more, granularity is larger, is difficult in catalyst field and field of batteries application, there are process flow complexity, equipment energy consumption height, ring
The problems such as border is seriously polluted, process control error is big, and process is not easy to control, causes powder size and pattern uncontrollable, causes
The variation of properties of product.
Gas phase reduction process is that nickel metallic solution and hydrocarbon containing oxygen atom are placed in hydrocarbon to burn
Reactor in decomposition-reduction prepare extra-fine nickel powder.Vapor phase method mainly includes wire electric blasting method, carbonyl nickel thermal decomposition
And vaporize-condensation law.The powder granularity wider distribution of wire electric blasting method preparation, steaming-condensation method production efficiency is low, and particle is easy
It aoxidizes and the device is complicated, it is expensive to be difficult to realize industrialize.
Normal pressure liquid phase reduction is under normal pressure to be coordinated nickel ion, nickel in aqueous solution or organic system with reducing agent
Solion or the reduction of insoluble compound, the method for obtaining nano nickel particles, compared with other methods, this method has equipment
Simply, various forms of raw materials can be used, it is excellent that powder diameter obtained is small, particle size distribution is narrow, chemical uniformity is good
Point, but its decomposition induction time is long, and powder granule is easy to reunite, and production cost is higher, and using a large amount of organic solvent as auxiliary
Auxiliary agent, as 102,554,259 102962470 A of A, CN of Chinese invention patent CN, CN01144702.8,
CN200710120159.7 and Japan Patent (the open flat 3257106.199l.11.15 of Application Publication (A)).Solid phase reduction method is
Solid-state displacement reaction directly occurs with reduction simple substance by metallic nickel to prepare extra-fine nickel powder, the production of nickel oxygen compound hydrogen reduction method
Nickel powder journey it is spherical or spherical, production technology is more complicated, and the homogeneity of product is poor, and granularity is larger, product Fei Shi
Degree is at 2-4 μm, and product profit is low, and in process of production, and safety and environmental protection problem is than more prominent.Gamma Rays method is water warp
Gamma Rays generate Primary product, and wherein reproducibility particle can restore step by step metallic nickel ions, and newly-generated nickle atom is poly-
Collection nucleation, ultimately generates nano particle.
Chinese invention patent CN02147855 discloses a kind of preparation method of fibrous nickel powder, using precipitating critical heat point
Solution Ni at normal temperature2+-NH3-NH4+-Cl--C2O4 2--H2The precursor synthesis process of nickel powder preparation, Yi Jihou are carried out in O system
Presoma is resolved into extra-fine nickel powder by continuous thermal decomposition process.Chinese invention patent CN03159577 disclose fibrous nickel powder with
The preparation method of nickel protoxide powder converts thermal decomposition method using precipitating, in Ni under normal temperature and pressure conditions2+-NH3-NH4+-Cl--
SGn--C2O4 2--H2Nickel powder or nickel protoxide powder presoma are synthesized in O system, are being aoxidized and are being thermally decomposed forerunner under non-oxidizing conditions
Fibrous nickel protoxide powder and fibrous nickel powder is finally made in body.Chinese invention patent CN03159577 discloses CN
104625082 A disclose a kind of preparation method of nanoscale nickel powder, by additive and surfactant realize different-shape,
The preparation of different-grain diameter extra-fine nickel powder.But above-mentioned patent shortcoming show respectively ammonium hydroxide environmental issue it is big, can not basis
Production needs that Reasonable Regulation And Control selection prepares extra-fine nickel powder/carbon composite and organic solvent is difficult.
The carbon material also common excellent conductive agent of water system power battery, makes with extra-fine nickel powder as composite material
With, it is possible to reduce water system power battery slurry arrangement step, but course grain, morphology controllable are prepared under no adjuvant,
There is not been reported in 0.06-1.2 μm of spherical ultra-fine nickel powder/carbon material report for prepared sizes.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of systems of water system power battery combined conductive agent
Preparation Method, prepares granularity, morphology controllable under no adjuvant, spherical ultra-fine nickel powder/carbon material of the granularity at 0.06-1.2 μm,
The requirement of water system power battery combined conductive agent is fully met, oxygen content is low, and properties of product are stablized.
The preparation method of water system power battery combined conductive agent of the present invention, using deionized water as reaction kettle
Bottom liquid, while nickel sulfate solution and sodium oxalate water solution is added, reaction generates amorphous precipitated nickel oxalate；Ageing, solid-liquid point
From obtaining filter cake；Filter cake is added in HPMC glue and is stirred into slurry；Slurry is spray-dried at spheric granules；It is spherical
Particle is using hydrogen reduction up to spherical ultra-fine nickel powder/carbon material.
Preferably, the preparation method of water system power battery combined conductive agent of the present invention, comprising the following steps:
(1) nickel sulfate and sodium oxalate are respectively configured as A liquid and B liquid with deionized water；
(2) A liquid and B liquid are added simultaneously as reaction kettle bottom liquid using deionized water, 6~10, reaction generates pH value
Amorphous precipitated nickel oxalate；
(3) after amorphous precipitated nickel oxalate ageing, filter cake is obtained through being separated by solid-liquid separation, then be washed with deionized water to neutrality；
(4) obtained solid is not necessarily to drying, is added directly into HPMC glue, is stirred evenly and be slurried using de-airing mixer
Material；
(5) slurry is spray-dried at spheric granules；
(6) spheric granules is using hydrogen reduction up to spherical ultra-fine nickel powder/carbon material.
Wherein:
The concentration of nickel sulfate is 1.5~2mol/L in A liquid in the step (1), and the concentration of B liquid mesoxalic acid sodium is 1.5
The concentration of~2mol/L, A liquid and B liquid ratio is 1:1, if nickel sulfate and sodium oxalate solution concentration are too high, nickel sulfate solution crystallization,
And higher temperature is needed to maintain solution state, increase energy consumption, if too low, product is very few in unit volume, and waste liquid increases.
Deionized water is the 5~10% of reactor volume.
The liquid velocity ratio of A liquid and B liquid in the step (2) is 100:100.1~100.5.In real reaction, sink
Shallow lake agent needs suitably excessively, to guarantee that nickel ion is converted to amorphous precipitated nickel oxalate form, therefore, sodium oxalate to greatest extent
The height of liquid velocity ratio nickel sulfate, but can not be too high, it is too high, sodium oxalate is caused to waste.
Step (2) reaction temperature is 30~40 DEG C, reaction time 4-8h；If temperature is too low, reaction speed compared with
Slowly, while the precipitating that generates belongs to unformed more, will cause subsequent filter difficulty and metal ion loss is big, if mistake
Height maintains the energy consumption of solution to increase, and reaction speed is too fast, and amorphous precipitated oxalic acid nickel particle nucleus is excessive, with the reaction time
Extend, nucleus is easy long greatly bulky grain, is unfavorable for using as conductive agent.
The slurry reacted in step (2) separates when reaching overflow port through cyclone, meets the discharge of granularity requirements, granularity is wanted
Ask at 0.5~0.9 μm, be unsatisfactory for granularity requirements back to the reaction was continued in reactor, achieve the purpose that continuously to synthesize.
The temperature being washed with deionized water in the step (3) is 80~95 DEG C, and washing times are 3~6 times.It is molten after ageing
Liquid is centrifuged as filter cake, and filter cake is washed.The deionized water of washing needs heating in advance, if temperature is too low,
Washing effect is not that very well, will increase washing times, but temperature can not be too high, and excessively high water temperature, operational danger increases, energy
Consumption also greatly increases, while the relevant device service life also greatly shortens；Washing times and filter cake thickness have relationship, are washed to filtrate
It is in neutrality.Further, since in continuous production, filtrate can be used for configuring without adding any adjuvant in Synthesis liquid
The bottom liquid of nickel sulfate, sodium oxalate solution and reaction kettle realizes that filtrate cycle uses, reduces production cost.
Solid masses content in the step (4) is 80~90%.
HPMC glue viscosity is 4000~20000mPa.s, and HPMC mass content is 3~6.5%, that is, HPMC glue
The mass content of middle HPMC is 3~6.5%, and the mass ratio of nickel oxalate and HPMC are 100:2~3.5.HPMC glue is by HPMC
With the glue of deionized water configuration, the HPMC binder of high-purity is made of carbon, hydrogen, oxygen, no other elements, according to subsequent spray
Required for drying, viscosity is in 4000~20000mPa.s, and low viscosity is conducive to manufacture bulky grain powder, and high viscosity is conducive to manufacture
Small particle powder, if viscosity is too low, solid content is relatively low, is also not easy preparation spherical shape, if viscosity is too high, energy consumption increases, no
It is easy to be atomized into spherical shape.Amorphous precipitated nickel oxalate is after washing in step (3), moisture content 10~20%, solid content 80
~90%, it is not necessarily to drying, is directly added into HPMC glue, needs to be adjusted with deionized water further according to viscosity.
The solid content of slurry is 60~70% in the step (4).
Spray drying are as follows: spraying furnace pressure is negative pressure, and spherical liquid is emitted into sprayer, at the same time, heating
Air spray, three-dimensional wink-dry is carried out to spherical liquid.
Preferably, it is spray-dried are as follows: spraying furnace pressure is negative pressure, and negative pressure is in -0.01~-0.015Mpa, in sprayer
In to rotate 20~45m/s of flow velocity be emitted into spherical liquid, at the same time, be heated to 130~175 DEG C of air with 30~75m/
The speed of s sprays, and carries out three-dimensional wink-dry to spherical liquid.Nickel oxalate is not afraid of the dioxygen oxidation in air, can directly make
It is dry with clean air.Spherical liquid direct balling shape powder under three-dimensional wink-dry.
Using hydrogen reduction are as follows: reducing atmosphere is the gaseous mixture of nitrogen and hydrogen, and volume ratio is 1:3~1:4, temperature 550
~650 DEG C, the recovery time is 4~8h.If hydrogen reduction temperature is too low, it is low to will cause production efficiency, and reduction is not thorough, and is made
It is higher at oxygen content；If reduction temperature is excessively high, the growth of extra-fine nickel powder particle will cause, particle is excessive.Recovery time control exists
In certain time, according to the arrangement of reduction furnace, boat is pushed away using single layer, 4h, using double-deck or three layers, 8h, in conjunction with
Hydrogen flow rate and flow, every boat containing quantity, requires to determine the specific time according to final products physical index.In reduction process
In, nickel oxalate is converted into extra-fine nickel powder, and HPMC is coated on extra-fine nickel powder surface, final product by thermally decomposing remaining carbon material
For spherical ultra-fine nickel powder/carbon material.
Obtained powder body material can carry out classification processing using cyclone classified equipment according to customer requirement.
Compared with prior art, the present invention having the following advantages and beneficial effects:
(1) spherical ultra-fine nickel powder/carbon material oxygen content obtained in the present invention is low, it can be achieved that industrialization, properties of product are steady
It is fixed, favorable reproducibility, and production process is nontoxic, pollution-free, it is compound to meet water system power battery for environmental-friendly, excellent product performance
The demand of conductive agent, alternative foreign countries' imported product, breaks foreign technology monopolization, makes up domestic technique blank.
(2) present invention prepares granularity, morphology controllable, spherical super fine nickel of the granularity at 0.06-1.2 μm under no adjuvant
Powder/carbon material fully meets the requirement of water system power battery combined conductive agent, reduces a water system power battery and slurry process
The number of conductive agent is added, and conductive agent mixing time reduces half, the uniformity improves 30%.Traditional mixing is because of carbon powder particle
Very thin, light specific gravity, specific surface are big, are easy to reunite, and need first to be uniformly mixed carbon dust before mixing, mix to break up, need
6~12h is stirred, nickel powder is then just added and is stirred, is uniformly mixed, and need 2~4h.Carbon dust and nickel powder material of the present invention
Compound, disposable mixing time is only 4~8h, reduces half.In addition, prior art carbon dust first stirs, because of specific surface area
Greatly, from heavy and light, the uniformity is only granular-grade, after nickel powder is added, since nickel powder is from heavy, is stirred on this basis, the uniformity is also
It is to rest on uniform in macroscopical volume, in milliliter volume, disperses less uniform, naked eyes are on a glass it can be seen that part
Particle agglomeration；And specific gravity of the present invention is suitable, very uniformly in advance, after some period of time, can produce collaboration uniformly effect
Fruit, reaches that molecule rank is uniform, and the particle of reunion reduces 30%, and the uniformity improves 30% or more.
(3) extra-fine nickel powder/carbon material prepared by the present invention has fully spherical shape structure, and particle surface is smooth, and partial size can
It controls and particle diameter distribution is narrow, inoxidizability is strong, good dispersion, average particle size are 60~1200nm.
(4) preparation process of the present invention does not need any adjuvant such as ammonium hydroxide, organic solvent etc., thoroughly eliminates from source dirty
Object is contaminated, subsequent wastewater treatment cost is reduced, meets green production process, there is important environment protection significance.
(5) extra-fine nickel powder/carbon material produced by the invention is spherical powder, laser particle size D50At 0.06~1.0 μm, BET
In 2~20m2/ g, 0.5~1.2g/cm of apparent density3, carbon is 2~3.5%, iron≤0.001%, sulphur≤0.01%, and oxygen≤
1.0%.
Detailed description of the invention
Fig. 1 is the process flow chart using the method for the present invention preparation water system power battery combined conductive agent；
Fig. 2 is the size distribution curve of product prepared by the embodiment of the present invention 3；
Fig. 3 is the pattern of product prepared by the embodiment of the present invention 3.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
Embodiment 1
(1) nickel sulfate and sodium oxalate are respectively configured as A liquid and B liquid with deionized water, concentration is 2mol/L；
(2) A liquid and B liquid are added simultaneously, the liquid velocity ratio of A liquid and B liquid using deionized water as reaction kettle bottom liquid
For 100:100.5,40 DEG C of synthesis temperature, for pH value 10, reaction generates amorphous precipitated nickel oxalate；Reaction solution reaches overflow port
When, overflow port valve is opened, the slurry that overflow goes out separates through cyclone separator, meets being expelled directly out for granularity requirements, do not meet
Granularity requirements back to the reaction was continued in reactor, achieve the purpose that continuously to synthesize.
(3) after amorphous precipitated nickel oxalate ageing, filter cake is obtained through being separated by solid-liquid separation, then be washed with deionized water to neutrality,
Middle deionization washing temperature is 95 DEG C, and washing times are 6 times；Filtrate after tested, returns as new nickel sulfate and newly
Sodium oxalate solution configuration.
(4) obtained solid is not necessarily to drying, and solid masses content 90% is added directly into HPMC glue, and HPMC glue is viscous
Degree is 20000mPa.s, and HPMC mass content is 6.5%, is stirred into slurry, the solid content of slurry using de-airing mixer
It is 60%, the mass ratio of nickel oxalate and HPMC are 100:3.5.
(5) spraying furnace pressure is negative pressure, is emitted into spherical liquid in sprayer with certain flow velocity, at the same time,
The air of heating is sprayed with corresponding speed, carries out three-dimensional wink-dry to spherical liquid, slurry is spray-dried at spherical
Grain；
(6) spheric granules uses hydrogen reduction, and hydrogen reduction temperature is 650 DEG C, and the recovery time is 4h to get spherical super fine nickel
Powder/carbon material.
Extra-fine nickel powder/carbon material that embodiment 1 obtains is spherical powder, laser particle size D50At 1.0 μm, BET is in 2m2/ g,
Apparent density 0.5g/cm3, carbon is 3.5%, iron≤0.001%, sulphur≤0.01%, oxygen≤1.0%.
Embodiment 2
(1) nickel sulfate and sodium oxalate are respectively configured as A liquid and B liquid with deionized water, concentration is 1.5mol/L；
(2) A liquid and B liquid are added simultaneously, the liquid velocity ratio of A liquid and B liquid using deionized water as reaction kettle bottom liquid
For 100:100.1,30 DEG C of synthesis temperature, for pH value 6, reaction generates amorphous precipitated nickel oxalate；Reaction solution reaches overflow port
When, overflow port valve is opened, the slurry that overflow goes out separates through cyclone separator, meets being expelled directly out for granularity requirements, do not meet
Granularity requirements back to the reaction was continued in reactor, achieve the purpose that continuously to synthesize.
(3) after amorphous precipitated nickel oxalate ageing, filter cake is obtained through being separated by solid-liquid separation, then be washed with deionized water to neutrality,
Middle deionization washing temperature is 80 DEG C, and washing times are 3 times；Filtrate after tested, returns as new nickel sulfate and newly
Sodium oxalate solution configuration.
(4) obtained solid is not necessarily to drying, and solid masses content 80% is added directly into HPMC glue, and HPMC glue is viscous
Degree is 4000mPa.s, and HPMC mass content is 3%, is stirred into slurry using de-airing mixer, the solid content of slurry is
70%, the mass ratio of nickel oxalate and HPMC are 100:2.
(5) spraying furnace pressure is negative pressure, is emitted into spherical liquid in sprayer with certain flow velocity, at the same time,
The air of heating is sprayed with corresponding speed, carries out three-dimensional wink-dry to spherical liquid, slurry is spray-dried at spherical
Grain；
(6) spheric granules uses hydrogen reduction, and hydrogen reduction temperature is 550 DEG C, and the recovery time is 8h to get spherical super fine nickel
Powder/carbon material.
Extra-fine nickel powder/carbon material that embodiment 2 obtains is spherical powder, and laser particle size D50 is at 0.06 μm, and BET is in 20m2/
G, apparent density 1.2g/cm3, carbon is 2%, iron≤0.001%, sulphur≤0.01%, oxygen≤1.0%.
Embodiment 3
(1) nickel sulfate and sodium oxalate are respectively configured as A liquid and B liquid with deionized water, concentration is 1.8mol/L；
(2) A liquid and B liquid are added simultaneously, the liquid velocity ratio of A liquid and B liquid using deionized water as reaction kettle bottom liquid
For 100:100.3,35 DEG C of synthesis temperature, for pH value 9, reaction generates amorphous precipitated nickel oxalate；Reaction solution reaches overflow port
When, overflow port valve is opened, the slurry that overflow goes out separates through cyclone separator, meets being expelled directly out for granularity requirements, do not meet
Granularity requirements back to the reaction was continued in reactor, achieve the purpose that continuously to synthesize.
(3) after amorphous precipitated nickel oxalate ageing, filter cake is obtained through being separated by solid-liquid separation, then be washed with deionized water to neutrality,
Middle deionization washing temperature is 85 DEG C, and washing times are 5 times；Filtrate after tested, returns as new nickel sulfate and newly
Sodium oxalate solution configuration.
(4) obtained solid is not necessarily to drying, and solid masses content 75% is added directly into HPMC glue, and HPMC glue is viscous
Degree is 15000mPa.s, and HPMC mass content is 5%, is stirred into slurry using de-airing mixer, the solid content of slurry is
66%, the mass ratio of nickel oxalate and HPMC are 100:2.8.
(5) spraying furnace pressure is negative pressure, is emitted into spherical liquid in sprayer with certain flow velocity, at the same time,
The air of heating is sprayed with corresponding speed, carries out three-dimensional wink-dry to spherical liquid, slurry is spray-dried at spherical
Grain；
(6) spheric granules uses hydrogen reduction, and hydrogen reduction temperature is 600 DEG C, and the recovery time is 6h to get spherical super fine nickel
Powder/carbon material.
Extra-fine nickel powder/carbon material that embodiment 3 obtains is spherical powder, laser particle size D50At 0.08 μm, BET is in 10m2/
G, apparent density 1.0g/cm3, carbon is 2.6%, iron≤0.001%, sulphur≤0.01%, oxygen≤1.0%.
Claims (9)
1. a kind of preparation method of water system power battery combined conductive agent, it is characterised in that: the following steps are included:
(1) nickel sulfate and sodium oxalate are respectively configured as A liquid and B liquid with deionized water；
(2) A liquid and B liquid are added simultaneously as reaction kettle bottom liquid using deionized water, 6~10, reaction is generated without fixed pH value
Type precipitates nickel oxalate；
(3) after amorphous precipitated nickel oxalate ageing, filter cake is obtained through being separated by solid-liquid separation, then be washed with deionized water to neutrality；
(4) obtained solid is not necessarily to drying, is added directly into HPMC glue, is stirred into slurry using de-airing mixer；
(5) slurry is spray-dried at spheric granules；
(6) spheric granules is using hydrogen reduction up to spherical ultra-fine nickel powder/carbon material.
2. the preparation method of water system power battery combined conductive agent according to claim 1, it is characterised in that: the step
Suddenly the concentration of nickel sulfate is 1.5~2mol/L in the A liquid in (1), and the concentration of B liquid mesoxalic acid sodium is 1.5~2mol/L, A liquid and B
The concentration ratio of liquid is 1:1.
3. the preparation method of water system power battery combined conductive agent according to claim 2, it is characterised in that: the step
Suddenly the liquid velocity ratio of the A liquid in (2) and B liquid is 100:100.1~100.5.
4. the preparation method of water system power battery combined conductive agent according to claim 1, it is characterised in that: the step
Suddenly (2) reaction temperature is 30~40 DEG C；The temperature being washed with deionized water in the step (3) is 80~95 DEG C, washing times 3
~6 times.
5. the preparation method of water system power battery combined conductive agent according to claim 1, it is characterised in that: the step
Suddenly the solid masses content in (4) is 80~90%；The solid content of slurry is 60~70%.
6. the preparation method of water system power battery combined conductive agent according to claim 1, it is characterised in that: HPMC glue
Water viscosity is 4000~20000mPa.s, and HPMC mass content is 3~6.5%, the mass ratio of nickel oxalate and HPMC be 100:2~
3.5。
7. the preparation method of water system power battery combined conductive agent according to claim 1, it is characterised in that: spraying dry
It is dry are as follows: spraying furnace pressure is negative pressure, and spherical liquid is emitted into sprayer, and at the same time, the air of heating sprays, to ball
Shape liquid carries out three-dimensional wink-dry.
8. the preparation method of water system power battery combined conductive agent according to claim 7, it is characterised in that: spraying dry
It is dry are as follows: spraying furnace pressure is negative pressure, and negative pressure is in -0.01~-0.015Mpa, to rotate 20~45m/s of flow velocity in sprayer
It is emitted into spherical liquid, at the same time, 130~175 DEG C of air is heated to and is sprayed with the speed of 30~75m/s, to spherical liquid
Body carries out three-dimensional wink-dry.
9. the preparation method of water system power battery combined conductive agent according to claim 1, it is characterised in that: use hydrogen
Reduction are as follows: reducing atmosphere is the gaseous mixture of nitrogen and hydrogen, and volume ratio is 1:3~1:4, and temperature is 550~650 DEG C, when reduction
Between be 4~8h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1491762A (en) * | 2002-10-22 | 2004-04-28 | 中南大学 | Process for preparing fibrous nickel powder |
| CN101428348A (en) * | 2008-07-29 | 2009-05-13 | 张建玲 | Process for producing spherical submicron metal with hydro-thermal treatment |
| CN102091789A (en) * | 2010-12-21 | 2011-06-15 | 丹阳市求精合金钢有限公司 | Method for preparing submicron hammer ball superfine nickel powder |
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2017
- 2017-05-31 CN CN201710405272.3A patent/CN107093743B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1491762A (en) * | 2002-10-22 | 2004-04-28 | 中南大学 | Process for preparing fibrous nickel powder |
| CN101428348A (en) * | 2008-07-29 | 2009-05-13 | 张建玲 | Process for producing spherical submicron metal with hydro-thermal treatment |
| CN102091789A (en) * | 2010-12-21 | 2011-06-15 | 丹阳市求精合金钢有限公司 | Method for preparing submicron hammer ball superfine nickel powder |
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