CN104505502B - Lithium titanate composite negative material for lithium ion battery and preparation method of lithium titanate composite negative material - Google Patents
Lithium titanate composite negative material for lithium ion battery and preparation method of lithium titanate composite negative material Download PDFInfo
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- CN104505502B CN104505502B CN201410827244.7A CN201410827244A CN104505502B CN 104505502 B CN104505502 B CN 104505502B CN 201410827244 A CN201410827244 A CN 201410827244A CN 104505502 B CN104505502 B CN 104505502B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium titanate composite negative material for a lithium ion battery and a preparation method of the lithium titanate composite negative material, and aims to improve the specific capacity, conductivity and high-rate charge/discharge characteristics of the negative material for the lithium ion battery. According to the lithium titanate composite negative material for the lithium ion battery disclosed by the invention, lithium titanate serves as a matrix, nano iron disulfide coats the matrix, the amount of the nano iron disulfide is 0.1-10.0 percent of the mass of the matrix, and the granularity of the lithium titanate composite negative material for the lithium ion battery is 0.5-18 microns. The preparation method comprises the following steps: preparing high-purity nano iron disulfide, mixing and sintering. Compared with the prior art, the lithium titanate composite negative material for the lithium ion battery disclosed by the invention has the advantages that the lithium titanate matrix is coated by nano iron disulfide, low conductivity of the lithium titanate material is effectively improved, the specific capacity and high-rate charge/discharge performance of the material are improved, the process is simple, the process flow is controllable, the production cost is low, the environmental pollution is avoided, and the service requirements on power and stored energy lithium ion batteries can be met.
Description
Technical field
The present invention relates to a kind of new energy materials and preparation method thereof, particularly a kind of lithium ion battery negative material and
Preparation method.
Background technology
Since the Sony nineties in 20th century realizes lithium ion battery commercial applications first, owing to it has higher
Energy density and good security performance, be used widely in the application such as electronic equipment and device.Graphite is as master
The lithium ion battery negative material wanted, has that theoretical gram volume is high, electron conduction good, the advantage of abundant raw material source, but
Still suffer from following deficiency: (1) during initial charge/discharge, graphite cathode Surface Creation one solid-electrolyte interface film
SEI, produces certain irreversible capacity.Along with continuing of cyclic process, SEI film can be continually changing, and makes graphitic carbon negative electrode material
Capacity reduce, cycle life decline；(2) some intermediate by-products generating SEI film can be inserted in the layer structure of graphite,
Cause structural collapse, limit electrolyte and the compatibility of solvent, the performance of suppression electrical property；(3) by more weak between graphite carbon-coating
Model ylid bloom action power connect, Li+Embedding and abjection can cause graphite cathode material structure expand and shrink, its rate of change
Being about 10%, this can make to separate between active material, loses the seriality of electronics conduction, cause service life between pole piece
Reduce with security performance.These problems of graphitic carbon material, greatly limit its in dynamical system and energy storage device field should
With.Therefore, people gradually invest alternative class non-carbon negative material sight.
There is the lithium titanate Li of cubic spinel type structure4Ti5O12Material, due to Stability Analysis of Structures, abundant raw material, safe nothing
Poison, has been developing progressively as the non-carbon negative material of most prospect in lithium ion battery material.Lithium titanate can make up graphitic carbon
Many deficiencies of negative material, are mainly manifested in: (1) lithium titanate platform voltage is 1.55V (1.55Vvs.Li/Li+), Bu Huiyu
Electrolyte reaction generates SEI film, and then it is low bad with safety to solve the cycle life caused because of the instability of SEI film own
Problem；(2) from complete discharge condition to charged state at full capacity, whole during Li4Ti5O12Material presents stable point all the time
Spar type structure, change in volume is less than 0.2%, is good " zero strain " material, can make the cycle performance of lithium ion battery
It is greatly improved, quick charge can be born.Additionally, lithium titanate anode material also has wider range of temperature range, especially
It is applicable to the anticathode materials'use requirements such as the transportation involved by power and energy-storage battery, electric tool and electrical network energy storage
Higher field.
But lithium titanate theoretical specific capacity is 175.0mAh/g, actual specific capacity is 160.0-165.0mAh/g, material
Energy density is relatively low.Lithium titanate anode material intrinsic conductivity is low simultaneously, and electrical conductivity is only 10-13S·cm-1, this makes lithium titanate electricity
Pond is in actual application, and under high current charge-discharge, capacity attenuation is too fast, and the performance of high rate performance is restricted.It addition, state
Inside and outside Li electricity enterprise currently mainly uses high temperature solid-state method to synthesize lithium titanate material, and the micron order material particle size prepared is distributed
Wide ranges, lack of homogeneity, compacted density is the most relatively low, carries out in charge and discharge process with electrolyte effect, Li+The evolving path is relatively
Long, be also unfavorable for the multiplying power property of battery and the performance of capacity, thus limit material means of transportation, electric tool power and
The scale application in the fields such as electrical network energy storage.For the problems referred to above, there is researcher to pass through metal ion mixing both at home and abroad, and lead
Conductive agent and the lithium titanate convergent improvements such as electricity white carbon black, CNT, Graphene, to improve the high rate performance and specific volume improving material
Amount.
The method of China Patent Publication No. CN102832382 A disclosed preparation nano-lithium titanate cathode material, reduces
Original position conductive coating in the reaction number of phases and course of reaction, to reach to suppress the purpose of crystal growth, this process to prepare
The lithium titanate anode material shortcoming that overcomes conventional high-temperature solid phase method so that it is narrow that lithium titanate material shows as on Nano grade
Distribution, improves the rate charge-discharge performance of material, but drawing abillity is poor.
Lithium titanate active material and preparation method thereof disclosed in China Patent Publication No. CN 102891302 A is with rechargeable
Electricity lithium battery, the problem that also refer to lithium titanate material low electric conductivity, use metal ion mixing, interpolation conductive agent carbon black to be blended
Method improve its electric conductivity, control synthesis technique simultaneously and prepare Nano grade lithium titanate material, with by reducing grain diameter
Shortening lithium ion the evolving path, the mode increasing electrolyte and conductive material contacts area improves battery charging and discharging power.But,
This method needs more binding agent to be bonded in foil substrate by lithium titanate active material, can reduce again the energy of battery electrode
Metric density.
The system of a kind of lithium ion battery silicon/lithium titanate anode material disclosed in China Patent Publication No. CN103794761 A
Preparation Method, using lithium titanate as matrix skeleton, introduces the silicon compound of Si oxide and other elements, prepares biphase uniform tool
Having high specific capacity and long circulation life silicon/lithium titanate composite material, material specific capacity can reach more than 500.0mAh/g, but
Shortcoming is that circulating effect is the best, and after using for a long time, capacity attenuation is very fast, and after 100 weeks, conservation rate is 82.9%.
In the transient metal sulfide with ferrous disulfide, copper sulfide, nickel sulfide, titanium disulfide etc. as representative, curing
The theoretical specific capacity of ferrum is up to 890mAh/g, far above the consumer battery material of existing market.Meanwhile, ferrous disulfide platform voltage
For 1.5V, close with lithium titanate material current potential, and in whole charge and discharge process, platform voltage is stable, without substantially polarization, greatly
Rate charge-discharge excellent performance.It addition, this material dissolubility in organic bath is the least, preferable electrochemistry can be kept
Activity.But the expansion rate of ferrous disulfide own is high, after iterative cycles, the embedding-abjection of lithium ion can produce Study of Volume Expansion,
Cause the too fast decay of capacity in cyclic process, thus reduce the useful life of lithium ion battery.
Summary of the invention
It is an object of the invention to provide a kind of lithium titanate composite negative electrode materials used by lithium ion batteries and preparation method thereof, solve
Technical problem is that certainly improves the specific capacity of lithium ion battery negative material, electric conductivity and high rate charge-discharge characteristic.
The present invention is by the following technical solutions: a kind of lithium titanate composite negative electrode materials used by lithium ion batteries, with lithium titanate is
Matrix, is coated with nanometer ferrous disulfide FeS at matrix2, nanometer curing iron is the 0.1～10.0% of substrate quality, institute
The granularity stating lithium titanate composite negative electrode materials used by lithium ion batteries is 0.5～18 μm.
The preparation method of a kind of lithium titanate composite negative electrode materials used by lithium ion batteries, comprises the following steps:
One, prepare high-purity nm ferrous disulfide, by the elemental mole ratios of composition ferrous disulfide, be 2.0～10.0 μ in granularity
The iron powder of m and purity be 99.9～99.99% sulfur powder in, add account for ferrous disulfide quality 0.1～the sodium chloride of 5.0%, right
The compound of iron powder, sulfur powder and sodium chloride carries out high-energy ball milling, and mill is situated between, the mass ratio of compound is 5～10:1, and rotating speed is 200
～500r/min, ball milling 24～72h, obtain ferrous disulfide material system；With hydrogen peroxide and sodium borohydride in mass ratio 0.2～
1.0:1 forms composite detergent, and composite detergent concentration of polymer solution is 5.0～35.0%, and ferrous disulfide material system is with multiple
Closing detergent solution mass ratio is 0.1～1.0:1, after soaking ferrous disulfide material system 1.0～2.5h, and washing, filter 23～5
Secondary, directly dry at 120～200 DEG C, obtain the high-purity nm ferrous disulfide that granularity is 20.0～50.0nm；
Two, mixing, by lithium, the mol ratio 0.7～1.0:1 of titanium, by the lithium source that granularity is 0.5～2.0 μm, granularity is 0.2
～2.5 titanium sources of μm, lithium source and titanium source gross mass 0.1～the high-purity nm ferrous disulfide of 10.0%, join containing dispersant
With in the aqueous solution of bonding agent, in aqueous solution, dispersant mass content is 1.0～25.0%, binding agent mass content be 0.1～
5.0%, lithium source and titanium source gross mass are 1:0.6～3.2 with the mass ratio of aqueous solution, zirconia ball with mix after the mass ratio expected
Being 5～10:1, rotating speed is 200～500r/min, ball milling 0.5～24h, obtains nanoscale and/or submicron order other ball milling slurry
Material；Described dispersant is more than one in dehydrated alcohol, ethylene glycol and glycerol；Described binding agent is carboxymethyl cellulose
More than one in sodium, butadiene-styrene rubber suspension and politef；Described lithium source is lithium carbonate, Lithium hydrate, lithium nitrate, vinegar
Acid lithium and Lithium Citrate de in more than one；Described titanium source is anatase titanium dioxide, rutile titanium dioxide, barium metatitanate
With more than one in titanium tetraisopropylate；
Three, sintering, is dried to obtain dry powder presoma, is 0.6～1.2m at flow3/h.M3Protective gas atmosphere under,
With the programming rate of 0.8～10.0 DEG C/min to 200～300 DEG C, presintering processes 2～5h, then with 0.5～10.0 DEG C/min
Programming rate to 600～800 DEG C, high temperature sintering processes after 2～25h, is naturally cooling to room temperature, obtains lithium ion battery in stove
Use lithium titanate composite anode material.
Pulverize after method step three sintering of the present invention, obtain the lithium ion battery metatitanic acid that granularity is 0.3～20.0 μm
Lithium composite negative pole material.
After the method for the present invention is pulverized, the speed of mainshaft is 700～1300r/min, and the material jolt ramming after pulverizing is processed 1.0
～6.0h, obtain the lithium titanate composite negative electrode materials used by lithium ion batteries that granularity is 0.5～18 μm.
The jolt ramming of the present invention processes and uses mechanical fusion machine.
The high-energy ball milling of the method step one of the present invention, mill is situated between and uses the zirconia ball of diameter of phi 0.5～Φ 5.0mm.
The immersion of the method step one of the present invention, ferrous disulfide material system with composite detergent solution quality ratio is
0.125～0.87:1.
The ball milling of the method step two of the present invention, zirconia ball uses the zirconia ball of diameter of phi 0.5～Φ 5.0mm.
The sintering of the method step three of the present invention, protective gas is more than one in nitrogen, argon and helium.
The pulverizing of the method step four of the present invention, uses jet mill, is 0.8～1.5MPa in pressure limit, frequency
It is 130～190Hz.
Compared with prior art, lithium titanate matrix is coated with nanometer ferrous disulfide to the present invention, effectively improves lithium titanate
Material low conductivity, improves its specific capacity and rate charge-discharge performance, and technique is simple, technical process is controlled, and production cost is low, right
Environmental nonpollution, it is possible to meet the use requirement of power and energy storage lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the SEM photograph () of the lithium titanate anode material of comparative example.
Fig. 2 is the SEM photograph () of the lithium titanate composite negative electrode materials used by lithium ion batteries of embodiment 2.
Fig. 3 is the SEM photograph (two) of the lithium titanate anode material of comparative example.
Fig. 4 is the SEM photograph (two) of the lithium titanate composite negative electrode materials used by lithium ion batteries of embodiment 2.
Detailed description of the invention
With embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings.The lithium ion battery metatitanic acid of the present invention
Lithium composite negative pole material (composite), with lithium titanate as matrix, is coated with nanometer ferrous disulfide FeS at matrix2, nanometer two
Sulfuration iron is the 0.1～10.0% of substrate quality, and the granularity of composite is 0.5～18 μm.
The preparation method of the lithium titanate composite negative electrode materials used by lithium ion batteries of the present invention, by controlling iron powder and sulfur powder
Ratio, after the two being blended, carries out high-energy ball milling, then through washing, filtration treatment, obtains high-purity nm ferrous disulfide.By lithium
Source, titanium source and high-purity nm ferrous disulfide mix, and through high temperature sintering and mechanical fusion, are formed with lithium titanate as matrix, receive
Rice ferrous disulfide is the composite of covering material.Specifically include following steps:
One, high-purity nm ferrous disulfide is prepared, under room temperature (20 DEG C), by composition ferrous disulfide FeS2Elemental mole ratios,
The iron powder that granularity is 2.0～10.0 μm and purity be 99.9～99.99% sulfur powder (sulfur simple substance) in, add account for FeS2Quality
0.1～the solid dispersion sodium chloride nacl of 5.0%, in politef ball grinder, with diameter of phi 0.5～Φ 5.0mm's
Zirconium oxide ball milling is situated between, and the compound of Fe powder, S powder and NaCl is carried out high-energy ball milling process, and mill is situated between, the mass ratio of compound is 5
～10:1, rotating speed is 200～500r/min, and ball milling 24～72h obtains ferrous disulfide FeS2Material system.
After high-energy ball milling processes, the ferrous disulfide material system obtained contains slightly solubility oxidation of impurities ferrum, curing
Silicon and aluminium sesquioxide, these impurity are mainly produced by Fe powder, S powder and NaCl raw material and ball milling preparation process.Use hydrogen peroxide
H2O2With sodium borohydride BH4The mix reagent of Na composition is composite detergent, H2O2With BH4Na mass ratio is 0.2～1.0:1, multiple
Closing detergent solution mass concentration is 5.0～35.0%.Ferrous disulfide material system is 0.1 with composite detergent solution quality ratio
～1.0:1, preferably 0.125～0.87:1, after soaking ferrous disulfide material system 1.0～2.5h, with pure water, filter 23
～5 times, directly to dry at 120～200 DEG C, remove impurity, prepared ferrous disulfide purity is not less than at 99.9%, then grinding
Reason removes caking, obtains the high-purity nm ferrous disulfide that granularity is 20.0～50.0nm.
High-energy ball milling is by broken for the Fe grinding that granularity is 2.0～10.0 μm so that it is possesses and forms binary compound with sulfur powder
Ability.Addition NaCl is used for slowing down nanorize effect in Process During High Energy Ball Milling and causes reunion to cause iron powder and sulfur powder dispersion inequality,
Inhibit the formation of FeSx (x ≠ 2) dephasign, promote FeS2The formation of crystal grain and growth, wash 3～5 with pure water by ball milling product
Secondary, remove the NaCl being mixed in ferrous disulfide.By the purpose of composite detergent solution soaking, it is that removing Conventional solvents is difficult to
Ferrum oxide, silicon disulfide and the aluminium sesquioxide impurity component dissolved, obtains spherical high-purity nm ferrous disulfide.
Two, mixing, under the conditions of 20 ± 5 DEG C, by lithium Li, the mol ratio 0.7～1.0:1 of titanium Ti, by granularity be 0.5～
The lithium source of 2.0 μm, granularity is the titanium source of 0.2～2.5 μm, lithium source and titanium source gross mass 0.1～high-purity nm two sulfur of 10.0%
Changing ferrum, join in the aqueous solution containing dispersant and bonding agent, in aqueous solution, dispersant mass content is 1.0～25.0%,
Binding agent mass content is 0.1～5.0%, and the mass ratio of lithium source and titanium source gross mass and aqueous solution is 1:0.6～3.2, stirring
Mix homogeneously, use planetary ball mill, diameter of phi 0.5～Φ 5.0mm zirconia ball with mix after expect mass ratio be 5～
10:1, is placed in polytetrafluoroethyltank tank, and rotating speed is 200～500r/min, and ball milling 0.5～24h obtains nanoscale and/or sub-micro
Meter level other ball milling slurry.
Dispersant is more than one in dehydrated alcohol, ethylene glycol and glycerol.
Binding agent is more than one in sodium carboxymethyl cellulose, butadiene-styrene rubber suspension and politef.
Lithium source is more than one in lithium carbonate, Lithium hydrate, lithium nitrate, lithium acetate and Lithium Citrate de.
Titanium source be one in anatase titanium dioxide, rutile titanium dioxide, barium metatitanate and titanium tetraisopropylate with
On.
In mechanical milling process, mill is situated between and mutually colliding between material, on the one hand can reduce lithium source and the granularity in titanium source, separately
On the one hand reduce the surface tension of solvent, increase ball milling slurry dispersing uniformity.
Three, sintering, by ball milling slurry under continuous stirring state, before obtaining dry powder with the spray dried form of prior art
Driving body, dry powder presoma is 0.6～1.2m at flow3/h.M3Protective gas atmosphere under, with the liter of 0.8～10.0 DEG C/min
Temperature speed is to 200～300 DEG C, and presintering processes 2～5h, then with the programming rate of 0.5～10.0 DEG C/min to 600～800
DEG C, after high temperature sintering processes 2～25h, in stove, it is naturally cooling to room temperature, obtains the lithium titanate material of ferrous disulfide cladding.
Protective gas is more than one in nitrogen, argon and helium.
High temperature sintering furnace is tube furnace, batch-type furnace, rotary furnace or tunnel cave.
Due to high-purity nm ferrous disulfide structure spherical in shape, smooth surface, there is stronger mobility.With lithium source, titanium source
Carry out presintering after mix homogeneously, remove volatile impurity and promote raw material to decompose.High temperature sintering induction lithium titanate crystal growth,
Form spinel type lithium titanate material, meanwhile, by FeS2It is coated to the surface of spinel type lithium titanate material granule, after cladding
Material surface has microcellular structure, plays and increases lithium ion diffusion coefficient and improve the effect of lithium titanate material high rate performance.
Four, pulverizing, use jet mill, be 0.8～1.5MPa in pressure limit, frequency is the condition of 130～190Hz
Under, the micropore lithium titanate primary material being coated with by ferrous disulfide is pulverized, or with mechanical ball grinding machine ball milling, obtain granularity be 0.3～
The comminuting matter of 20.0 μm.
Mechanical ball grinding machine is planetary mechanical ball grinding machine, tumbling ball mill or stirring ball mill.
Five, merging, use mechanical fusion machine, be 6.0L at volume, the speed of mainshaft is 700～1300r/min, to ground product
Material jolt ramming processes 1.0～6.0h, obtains the lithium titanate composite negative electrode materials used by lithium ion batteries that granularity is 0.5～18 μm, with titanium
Acid lithium is matrix, and matrix is coated with lithium titanate and the ferrous disulfide composite negative pole material of nanometer ferrous disulfide.
Comminuting matter, in a device through the mechanofusion process repeatedly extruding, shearing and mutually collide, will agglomerate into
Second particle break up, and discharge the air in material, volatility atmosphere and/or impurity, form mixing and dispersion effect is good
Material granule.
The present invention, by high-purity nm ferrous disulfide is coated to lithium titanate surface, utilizes high-purity nm ferrous disulfide modified
The performance of lithium titanate anode material, play " zero strain " structural advantage and the ferrous disulfide height ratio capacity of lithium titanate material, big times
Rate charge-discharge characteristic, effectively improves lithium titanate material low conductivity, improves specific capacity and the rate charge-discharge of lithium titanate material
Performance, has the feature of high connductivity, height ratio capacity, long circulating and high rate charge-discharge.The preparation method of the present invention obtains technique letter
List, process control, low production cost, environmentally safe.
Compared to not doing the lithium titanate material of modification, high-purity nm ferrous disulfide cladding lithium titanate is modified, compound
Material relatively lithium titanate matrix surface void significantly reduces.This is coated on lithium titanate matrix mainly due to high-purity nm ferrous disulfide
Surface, adds structural compactness and the compactness of composite, and composite material surface becomes than uncoated high-purity nm two sulfur
Change before ferrum more smooth and smooth.
Lithium titanate composite negative electrode materials used by lithium ion batteries embodiment prepared, uses Jeol Ltd.
The JSM-6610A type scanning electron microscope detection pattern of JEOL, by the BT-9300Z intelligence of Dandong Bai Te Instrument Ltd.
Laser particle size analyzer records particle mean size, records jolt ramming by the TAP-2S tap density meter of Lu root instrument (Zhenjiang) company limited
Density, records powder body compacted density with the 4350 compacted density instrument of card not (Carver) company of the U.S., uses U.S. Kang Ta
The full-automatic specific surface area of NOVA4000E of Quantachrome company and porosity Sorption Analyzer record specific surface area.Use
State identical instrument and record the granularity of comparative example gained negative material, tap density, compacted density and specific surface area.Test result
It is shown in Table 1.
The lithium titanate composite negative electrode materials used by lithium ion batteries that embodiment is prepared and comparative example gained negative material,
On the CT2001A type cell tester that Wuhan City indigo plant electricity electronics LAND company limited produces, half is carried out as negative electrode active material
Battery simulation test.After negative electrode active material, conductive black mix according to the mass ratio of 90:5:5 with binding agent, it is coated in aluminium foil
On matrix, 120 DEG C of dried 5h, roll the circular pole piece cut out in Φ 14mm, protect (O at high-purity argon gas2≤ 0.5ppm, H2O
≤ 0.5ppm) Braun MBRAUN glove box in, with metal lithium sheet for electrode, barrier film is Celgard2400, and electrolyte is
1mol·L-1LiPF6/DMC+DEC+EC (volume ratio is 1:1:1) is assembled into CR2025 button cell.Charging/discharging voltage scope is
0.8-2.7V.Specific capacity first is tested with 0.1C, 1C, 3C, 5C and 10C multiplying power, the efficiency first of 3C multiplying power, 5C and 10C multiplying power
Capability retention after circulation in 50 weeks.Test result is shown in Table 2-table 4.
Embodiment 1
One, high-purity nm ferrous disulfide is prepared, by the sulfur powder that Fe powder 233.0g that granularity is 2.0 μm, purity are 99.95%
267.0g, 12.5gNaCl (account for FeS2Quality 2.5%) in the politef ball grinder, add 2.5Kg, diameter of phi 0.5mm
Zirconium oxide ball milling is situated between, and mill is situated between, the mass ratio of compound is 5:1, under conditions of rotating speed is 200r/min, and ball-milling treatment 72h,
To ferrous disulfide FeS2Material system.
To ferrous disulfide FeS2Material system adds the compound washing agent solution that 4.0Kg mass concentration is 5.0%, peroxidating
Hydrogen 33.3g, sodium borohydride 166.7g, mass ratio is 0.2:1, and ferrous disulfide material system with composite detergent solution quality ratio is
0.125:1, soaks 1.5h, with pure water, filter 23, dries at 150 DEG C, and ferrous disulfide purity is not less than 99.9%, with grinding
Mill processes removes caking, obtains the high-purity nm ferrous disulfide that D50 granularity is 35.0nm.
Two, according to lithium Li, the ratio of titanium Ti mol ratio 0.87:1, lithium carbonate 162.0g, 0.2 μ that granularity is 0.5 μm are weighed
The anatase titanium dioxide 402.6g of m, lithium carbonate and the high-purity nm ferrous disulfide 0.5g of titanium dioxide gross mass 0.1%, add
Enter in the aqueous solution that 1.6Kg dehydrated alcohol content is 1.0% and carboxymethylcellulosodium sodium content is 0.1% stirring mixing, lithium
The mass ratio of source and titanium source gross mass and aqueous solution is 1:3.2, uses planetary type ball-milling technique, selects the oxygen of diameter of phi 3.0mm
Change zirconium mill Jie 2.5Kg, zirconia ball with mix after expect mass ratio be 5:1, with the rotating speed ball milling 5h of 200r/min, obtain ball milling
Slurry.
Three, by ball milling slurry under continuous stirring state, it is spray-dried and obtains dry powder presoma.Nitrogen flow is 0.6m3/
h.M3Protective atmosphere under, be first warming up to 200 DEG C with the programming rate of 0.8 DEG C/min in batch-type furnace, presintering processes 2h.So
After with the programming rate of 0.5 DEG C/min to 800 DEG C, high temperature sintering processes 25h, is naturally cooling to room temperature, obtains curing in stove
The lithium titanate material of ferrum cladding.
Four, pulverizing, use jet mill, pressure is 0.8MPa, and frequency is 130Hz, and obtaining granularity is 0.3～17.0 μm
Comminuting matter.
Five, merging, be 6.0L at volume, the speed of mainshaft is 1300r/min, comminuting matter jolt ramming is processed 1.0h, obtains
Particle mean size be 1.72 μm, tap density be 1.07g/cm3, compacted density is 1.78g/cm3, specific surface area is 3.22m2/ g's
Lithium titanate composite negative electrode materials used by lithium ion batteries, is shown in Table 1.
Embodiment 1 gained lithium titanate composite negative electrode materials used by lithium ion batteries is carried out on LAND cell tester half electricity
Pond simulation test, tests with 0.1C multiplying power, and specific capacity is 171.8mAh/g first, and efficiency is 99.5% first, after circulation in 50 weeks,
Specific capacity is 169.7mAh/g, and conservation rate is 98.8%.Meanwhile, test for 1C, 3C, 5C and 10C multiplying power, first specific volume
Amount is respectively 163.4mAh/g, 153.2mAh/g, 146.5mAh/g and 139.5mAh/g, first efficiency be 99.1%, 98.6%,
98.2% and 99.2%.After circulation in 50 weeks, its specific capacity conservation rate is 98.2%, 97.6%, 96.5% and 95.3%.This enforcement
Lithium titanate composite negative electrode materials used by lithium ion batteries specific capacity prepared by example is higher than lithium titanate theoretical specific capacity 175.0mAh/g, tool
There is preferable high rate performance, be shown in Table 2-table 4.
Embodiment 2
One, high-purity nm ferrous disulfide is prepared, by the sulfur powder that Fe powder 233.0g that granularity is 2.0 μm, purity are 99.95%
267.0g, 25.0gNaCl (account for FeS2Quality 5.0%) in the politef ball grinder, add 5.0Kg, diameter of phi 0.5mm
Zirconium oxide zirconium oxide ball milling is situated between, and mill is situated between, the mass ratio of compound is 10:1, under conditions of rotating speed is 500r/min, at ball milling
Reason 72h, obtains ferrous disulfide FeS2Material system.
To ferrous disulfide FeS2Material system adds the compound washing agent solution that 0.57Kg mass concentration is 35.0%, peroxide
Changing hydrogen 100.0g, sodium borohydride 100.0g, mass ratio is 1:1, ferrous disulfide material system and composite detergent solution quality ratio
For 0.87:1, soaking 2.5h, with pure water, filter 5 times, dry at 200 DEG C, ferrous disulfide purity is not less than 99.9%, uses
Milled processed removes caking, obtains the high-purity nm ferrous disulfide that D50 granularity is 20.5nm.
Two, according to lithium Li, the ratio of titanium Ti mol ratio 0.87:1, lithium carbonate 162.0g, 2.5 μ that granularity is 2.0 μm are weighed
The high-purity nm ferrous disulfide of the rutile titanium dioxide 402.6g of m, lithium carbonate and titanium dioxide gross mass 10.0%
50.0g, join 1.6Kg dehydrated alcohol content be 25.0% and carboxymethylcellulosodium sodium content be in 5.0% aqueous solution stir
Mixing, lithium source and titanium source gross mass are 1:3.2 with the mass ratio of aqueous solution, use planetary type ball-milling technique, use diameter of phi
3.0mm zirconium oxide mill Jie 2.5Kg, zirconia ball with mix after expect mass ratio be 5:1, with the rotating speed ball milling of 500r/min
5h, obtains ball milling slurry.
Three, by ball milling slurry under continuous stirring state, it is spray-dried and obtains dry powder presoma.Nitrogen flow is 0.6m3/
h.M3Protective atmosphere under, be first warming up to 300 DEG C with the programming rate of 10.0 DEG C/min in tube furnace, presintering processes 2h.
Then with the programming rate of 10.0 DEG C/min to 800 DEG C, high temperature sintering processes 25h, is naturally cooling to room temperature, obtains two sulfur in stove
Change the lithium titanate material of ferrum cladding.
Four, pulverizing, use jet mill, pressure is 1.5MPa, and frequency is 130Hz, and obtaining granularity is 0.5～19.0 μm
Comminuting matter.
Five, merging, be 6.0L at volume, the speed of mainshaft is 700r/min, comminuting matter jolt ramming is processed 6.0h, is put down
All granularities are 1.95 μm, and tap density is 1.25g/cm3, compacted density is 1.95g/cm3, specific surface area is 2.92m2The lithium of/g
Ion battery lithium titanate composite anode material, is shown in Table 1.
As shown in Figure 2 and Figure 4, processing through mechanical fusion, the granularity of composite negative pole material and distribution do not occur substantially to become
Changing, granule-morphology is still that class is spherical.Use ferrous disulfide cladding lithium titanate matrix, by increasing capacitance it is possible to increase the structural compactness of composite
And compactness, improve the bulk density of granule, meanwhile, make composite material surface become more smooth and smooth.
The composite active material obtaining embodiment 2 carries out the most forthright and cycle performance test, through 0.1C multiplying power
Test, specific capacity is 238.5mAh/g first, and efficiency is 99.2% first, and after circulation in 50 weeks, specific capacity is 234.4mAh/g, protects
Holdup is 98.3%., test for 1C, 3C, 5C and 10C multiplying power meanwhile, first specific capacity be respectively 229.7mAh/g,
218.9mAh/g, 210.9mAh/g and 202.8mAh/g, efficiency is 98.5%, 98.7%, 99.1% and 98.9% first.50 weeks
After circulation, its specific capacity conservation rate is 98.5%, 97.9%, 97.2% and 96.4%.Lithium ion battery prepared by the present embodiment
By lithium titanate composite anode material specific capacity higher than lithium titanate theoretical specific capacity 175.0mAh/g, there is preferable high rate performance,
It is shown in Table 2-table 4.
Embodiment 3
One, high-purity nm ferrous disulfide is prepared, by the sulfur powder that Fe powder 233.0g that granularity is 10.0 μm, purity are 99.9%
267.0g, 0.5gNaCl (account for FeS2Quality 0.1%) in the politef ball grinder, add 3.75Kg, diameter of phi 5.0mm
Zirconium oxide ball milling is situated between, and mill is situated between, the mass ratio of compound is 7.5:1, under conditions of rotating speed is 500r/min, and ball-milling treatment 24h,
Obtain ferrous disulfide FeS2Material system.
To ferrous disulfide FeS2Material system adds the compound washing agent solution that 4.0Kg mass concentration is 5.0%, peroxidating
Hydrogen 33.3g, sodium borohydride 166.7g, mass ratio is 0.2:1, and ferrous disulfide material system with composite detergent solution quality ratio is
0.125:1, soaks 1.5h, with pure water, filter 23, dries at 150 DEG C, and ferrous disulfide purity is not less than 99.9%, with grinding
Mill processes removes caking, obtains the high-purity nm ferrous disulfide that D50 granularity is 40.0nm.
Two, according to lithium Li, the ratio of titanium Ti mol ratio 0.70:1, weigh Lithium hydrate 142.5g that granularity is 0.5 μm,
The barium metatitanate 357.5g of 0.2 μm, Lithium hydrate and the high-purity nm ferrous disulfide 25.0g of barium metatitanate gross mass 5.0%, add
Entering in the aqueous solution that 0.3Kg ethylene glycol is 13.0% and butadiene-styrene rubber suspension is 0.1% stirring mixing, lithium source and titanium source are total
Quality is 1:0.6 with the mass ratio of aqueous solution, uses planetary type ball-milling technique, uses the zirconium oxide mill of 5.0Kg diameter of phi 0.5mm
Being situated between, after grinding Jie and mixing, the mass ratio of material is 10:1, with the rotating speed ball milling 24h of 200r/min, obtains ball milling slurry.
Three, by ball milling slurry under continuous stirring state, it is spray-dried and obtains dry powder presoma.Argon flow amount is 1.2m3/
h.M3Protective atmosphere under, be first warming up to 200 DEG C with the programming rate of 0.8 DEG C/min in rotary furnace, presintering processes 5h.So
After with the programming rate of 0.5 DEG C/min to 600 DEG C, high temperature sintering processes 2h, is naturally cooling to room temperature, obtains ferrous disulfide in stove
The lithium titanate material of cladding.
Four, pulverizing, use jet mill, pressure is 0.8MPa, and frequency is 190Hz, and obtaining granularity is 0.4～18.5 μm
Comminuting matter.
Five, merging, be 6.0L at volume, the speed of mainshaft is 1300r/min, comminuting matter jolt ramming is processed 1.0h, obtains
Particle mean size is 1.92 μm, and tap density is 1.20g/cm3, compacted density is 1.89g/cm3, specific surface area is 3.05m2/ g's
Lithium titanate composite negative electrode materials used by lithium ion batteries, is shown in Table 1.
The composite active material obtaining embodiment 3 carries out the most forthright and cycle performance test, through 0.1C multiplying power
Test, specific capacity is 215.2mAh/g first, and efficiency is 99.2% first, and after circulation in 50 weeks, specific capacity is 210.7mAh/g, protects
Holdup is 97.9%., test for 1C, 3C, 5C and 10C multiplying power meanwhile, first specific capacity be respectively 206.5mAh/g,
197.2mAh/g, 190.5mAh/g and 183.2mAh/g, efficiency is 98.6%, 98.9%, 99.1% and 98.4% first.50 weeks
After circulation, its specific capacity conservation rate is respectively 98.9%, 98.5%, 98.2% and 97.8%.Compare, embodiment 1 and enforcement 2,
The each rate capability of the present embodiment is the highest, keeps high efficiency first and high circulation volume conservation rate simultaneously, is shown in Table 2-table 4.
Embodiment 4
One, high-purity nm ferrous disulfide is prepared, by the sulfur powder that Fe powder 233.0g that granularity is 10.0 μm, purity are 99.9%
267.0g, 12.5gNaCl (account for FeS2Quality 2.5%) in the politef ball grinder, add 2.5Kg, diameter of phi 5.0mm
Zirconium oxide ball milling is situated between, and mill is situated between, the mass ratio of compound is 5:1, under conditions of rotating speed is 200r/min, and ball-milling treatment 72h,
To ferrous disulfide FeS2Material system.
To ferrous disulfide FeS2Material system adds the compound washing agent solution that 0.57Kg mass concentration is 35.0%, peroxide
Changing hydrogen 100.0g, sodium borohydride 100.0g, mass ratio is 1:1, ferrous disulfide material system and composite detergent solution quality ratio
For 0.87:1, soaking 2.5h, with pure water, filter 5 times, dry at 200 DEG C, ferrous disulfide purity is not less than 99.9%, uses
Milled processed removes caking, obtains the high-purity nm ferrous disulfide that D50 granularity is 20.0nm.
Two, according to lithium Li, the ratio of titanium Ti mol ratio 0.7:1, weigh Lithium hydrate 1142.5g that granularity is 2.0 μm,
The high-purity nm ferrous disulfide of the titanium tetraisopropylate 357.5g of 2.5 μm, Lithium hydrate and titanium tetraisopropylate gross mass 2.5%
12.5g, joins in the aqueous solution that 0.3Kg ethylene glycol content is 13.0% and butadiene-styrene rubber suspension content is 5.0% and stirs
Mixing, lithium source and titanium source gross mass are 1:0.6 with the mass ratio of aqueous solution, use planetary type ball-milling technique, use 5.0Kg diameter of phi
The zirconia ball of 0.5mm, after grinding Jie and mixing, the mass ratio of material is 10:1, with the rotating speed ball milling 24h of 500r/min, obtains ball milling
Slurry.
Three, by ball milling slurry under continuous stirring state, it is spray-dried and obtains dry powder presoma.Argon flow amount is 1.2m3/
h.M3Protective atmosphere under, in tunnel cave, be first warming up to 300 DEG C with the programming rate of 10.0 DEG C/min, presintering processes
5h.Then with the programming rate of 10.0 DEG C/min to 600 DEG C, high temperature sintering processes 2h, is naturally cooling to room temperature, obtains two in stove
The lithium titanate material of iron sulfide cladding.
Four, pulverizing, use jet mill, pressure is 1.5MPa, and frequency is 190Hz, and obtaining granularity is 0.6～19.0 μm
Comminuting matter.
Five, merging, be 6.0L at volume, the speed of mainshaft is 700r/min, comminuting matter jolt ramming is processed 6.0h, is put down
All granularities are 1.89 μm, and tap density is 1.15g/cm3, compacted density is 1.87g/cm3, specific surface area is 3.17m2The lithium of/g
Ion battery lithium titanate composite anode material, is shown in Table 1.
The composite active material obtaining embodiment 4 carries out the most forthright and cycle performance test, through 0.1C multiplying power
Test, specific capacity is 192.7mAh/g first, and efficiency is 97.5% first, and after circulation in 50 weeks, specific capacity is 190.2mAh/g, protects
Holdup is 98.7%., test for 1C, 3C, 5C and 10C multiplying power meanwhile, first specific capacity be respectively 184.8mAh/g,
173.9mAh/g, 166.8mAh/g and 159.9mAh/g, efficiency is 97.9%, 97.2%, 96.9% and 96.7% first.50 weeks
After circulation, its specific capacity conservation rate is respectively 98.5%, 98.3%, 97.9% and 96.5%.The lithium ion that the present embodiment obtains
Battery lithium titanate composite anode material, still has higher specific capacity and efficiency first, and high rate performance is still due to unmodified place
The lithium titanate anode material of reason, is shown in Table 2-table 4.
Embodiment 5
One, high-purity nm ferrous disulfide is prepared, by the sulfur powder that Fe powder 233.0g that granularity is 6.0 μm, purity are 99.99%
267.0g, 25.0gNaCl (account for FeS2Quality 5.0%) in the politef ball grinder, add 5.0Kg, diameter of phi 2.5mm
Zirconium oxide ball milling is situated between, and mill is situated between, the mass ratio of compound is 10:1, under conditions of rotating speed is 350r/min, and ball-milling treatment 48h,
Obtain ferrous disulfide FeS2Material system.
To ferrous disulfide FeS2Material system adds the compound washing agent solution that 1.0Kg mass concentration is 20.0%, peroxide
Changing hydrogen 75.0g, sodium borohydride 125.0g, mass ratio is 0.6:1, ferrous disulfide material system and composite detergent solution quality ratio
For 0.5:1, soaking 1.0h, with pure water, filter 4 times, dry at 120 DEG C, ferrous disulfide purity is not less than 99.9%, with grinding
Mill processes removes caking, obtains the high-purity nm ferrous disulfide that D50 granularity is 30.0nm.
Two, according to lithium Li, the ratio of titanium Ti mol ratio 1.0:1, by lithium acetate 184.6g that granularity is 1.3 μm, 1.4 μm
Anatase titanium dioxide 315.4g, lithium acetate and the high-purity nm ferrous disulfide 37.5g of titanium dioxide gross mass 7.5%, add
Stirring mixing, lithium source and titanium source in the aqueous solution that 0.95Kg glycerol content is 1.0% and polytetrafluoroethylene content is 2.5%
Gross mass is 1:1.9 with the mass ratio of aqueous solution, uses planetary type ball-milling technique, by the zirconium oxide of 3.75Kg diameter of phi 5.0mm
After grinding Jie and mixing, the mass ratio of material is 7.5:1, with the rotating speed ball milling 0.5h of 350r/min, obtains ball milling slurry.
Three, by ball milling slurry under continuous stirring state, it is spray-dried and obtains dry powder presoma.Helium gas flow is 0.9m3/
h.M3Protective atmosphere under, be first warming up to 250 DEG C with the programming rate of 6.0 DEG C/min in batch-type furnace, presintering processes 3.5h.
Then with the programming rate of 6.0 DEG C/min to 700 DEG C, high temperature sintering processes 14h, is naturally cooling to room temperature, obtains two sulfur in stove
Change the lithium titanate material of ferrum cladding.
Four, pulverizing, use jet mill, pressure is 1.0MPa, and frequency is 160Hz, and obtaining granularity is 0.5～18.2 μm
Comminuting matter.
Five, merging, be 6.0L at volume, the speed of mainshaft is 1000r/min, comminuting matter jolt ramming is processed 3.5h, obtains
Particle mean size is 1.90 μm, and tap density is 1.18g/cm3, compacted density is 1.89g/cm3, specific surface area is 3.03m2/ g's
Lithium titanate composite negative electrode materials used by lithium ion batteries, is shown in Table 1.
The composite active material obtaining embodiment 5 carries out the most forthright and cycle performance test, through 0.1C multiplying power
Test, specific capacity is 235.6mAh/g first, and efficiency is 99.7% first, and after circulation in 50 weeks, specific capacity is 233.2mAh/g, protects
Holdup is 99.0%., test for 1C, 3C, 5C and 10C multiplying power meanwhile, first specific capacity be respectively 227.2mAh/g,
216.8mAh/g, 209.6mAh/g and 202.4mAh/g, efficiency is 99.5%, 99.3%, 99.3% and 98.9% first.50 weeks
After circulation, its specific capacity conservation rate is respectively 98.9%, 98.5%, 97.8% and 96.8%, is shown in Table 2-table 4.
Embodiment 6
One, high-purity nm ferrous disulfide is prepared, by the sulfur powder that Fe powder 233.0g that granularity is 6.0 μm, purity are 99.99%
267.0g, 0.5gNaCl (account for FeS2Quality 0.1%) in the politef ball grinder, add 3.75Kg, diameter of phi 2.5mm
Zirconium oxide ball milling is situated between, and mill is situated between, the mass ratio of compound is 7.5:1, under conditions of rotating speed is 350r/min, and ball-milling treatment 48h,
Obtain ferrous disulfide FeS2Material system.
To ferrous disulfide FeS2Material system adds the compound washing agent solution that 1.0Kg mass concentration is 20.0%, peroxide
Changing hydrogen 75.0g, sodium borohydride 125.0g, mass ratio is 0.6:1, ferrous disulfide material system and composite detergent solution quality ratio
For 0.5:1, soaking 1.0h, with pure water, filter 4 times, dry at 120 DEG C, ferrous disulfide purity is not less than 99.9%, with grinding
Mill processes removes caking, obtains the high-purity nm ferrous disulfide that D50 granularity is 35.0nm
Two, according to lithium Li, the ratio of titanium Ti mol ratio 1.0:1, by Lithium Citrate de 184.6g that granularity is 1.3 μm, 1.4 μm
Rutile titanium dioxide 315.4g, the high-purity nm ferrous disulfide of Lithium Citrate de and titanium dioxide gross mass 7.5%
37.5g, joins stirring in the aqueous solution that 0.95Kg glycerol content is 25.0% and polytetrafluoroethylene content is 2.5% mixed
Closing, the mass ratio of lithium source and titanium source gross mass and aqueous solution is 1:1.9, uses planetary type ball-milling technique, a diameter of by 3.75Kg
The mass ratio that the zirconium oxide of Φ 5.0mm is expected after grinding Jie and mixing is 7.5:1, with the rotating speed ball milling 0.5h of 350r/min, obtains ball
Defibrination material.
Three, by ball milling slurry under continuous stirring state, it is spray-dried and obtains dry powder presoma.Helium gas flow is 0.9m3/
h.M3Protective atmosphere under, be first warming up to 250 DEG C with the programming rate of 6.0 DEG C/min in batch-type furnace, presintering processes 3.5h.
Then with the programming rate of 6.0 DEG C/min to 700 DEG C, high temperature sintering processes 14h, is naturally cooling to room temperature, obtains two sulfur in stove
Change the lithium titanate material of ferrum cladding.
Four, pulverizing, use jet mill, pressure is 1.0MPa, and frequency is 160Hz, and obtaining granularity is 0.7～15.4 μm
Comminuting matter.
Five, merging, be 6.0L at volume, the speed of mainshaft is 1000r/min, comminuting matter jolt ramming is processed 3.5h, obtains
Particle mean size is 1.89 μm, and tap density is 1.16g/cm3, compacted density is 1.87g/cm3, specific surface area is 3.04m2/ g's
Lithium titanate composite negative electrode materials used by lithium ion batteries, is shown in Table 1.
The composite active material obtaining embodiment 6 carries out the most forthright and cycle performance test, through 0.1C multiplying power
Test, specific capacity is 237.4mAh/g first, and efficiency is 99.5% first, and after circulation in 50 weeks, specific capacity is 235.5mAh/g, protects
Holdup is 99.2%., test for 1C, 3C, 5C and 10C multiplying power meanwhile, first specific capacity be respectively 229.5mAh/g,
218.4mAh/g, 210.6mAh/g and 203.8mAh/g, efficiency is 99.0%, 98.9%, 98.7% and 99.0% first.50 weeks
After circulation, its specific capacity conservation rate is respectively 98.7%, 98.4%, 98.4% and 97.2%, is shown in Table 2-table 4.
Comparative example
One, according to lithium Li, the ratio of titanium Ti mol ratio 0.87:1, lithium carbonate 162.0g, 1.4 μ that granularity is 1.3 μm are weighed
The anatase titanium dioxide 402.6g of m, joining 0.95Kg dehydrated alcohol content is 13.0% and carboxymethylcellulosodium sodium content
It it is stirring mixing in the aqueous solution of 2.5%.Use planetary type ball-milling technique, grind by the zirconium oxide of 3.75Kg a diameter of Φ 2.5mm
Be situated between with mix after the mass ratio expected be 7.5:1, with the rotating speed ball grinding mill of 350r/min process 24h, obtain ball milling slurry.
Two, spray drying obtains dry powder presoma.Nitrogen flow is 0.9m3/h.M3Protective atmosphere under, in batch-type furnace
First being warming up to 250 DEG C with the programming rate of 6.0 DEG C/min, presintering processes 3.5h.Then with the programming rate of 6.0 DEG C/min extremely
700 DEG C, high temperature sintering processes 14h, is naturally cooling to room temperature, obtains micropore lithium titanate primary material in stove.
Three, using jet mill, pressure is 0.85MPa, and frequency is 130Hz.
Four, being 6.0L at volume, the mechanical fusion machine speed of mainshaft is 1300r/min, and comminuting matter jolt ramming is processed 1.0h,
Obtaining particle mean size is 1.67 μm, and tap density is 1.02g/cm3, compacted density is 1.72g/cm3, specific surface area is 3.28m2/
The negative material of g, is shown in Table 1.
As shown in figures 1 and 3, processing through comminution by gas stream and mechanical fusion, material granule is submicrometer structure, and granularity
Distribution is more concentrated.But, owing to preparation process existing agglomeration, cause material course of reaction to locally lie in insufficient,
Degree of crystallinity is the highest, causes surface to there is more loose hole.
The negative material active substance obtaining comparative example carries out the most forthright and cycle performance test, surveys through 0.1C multiplying power
Examination, tests through 0.1C multiplying power, and specific capacity is 170.6mAh/g first, and efficiency is 99.2% first, after circulation in 50 weeks, and specific capacity
For 169.2mAh/g, conservation rate is 99.2%., testing for 1C, 3C, 5C and 10C multiplying power, specific capacity is respectively first meanwhile
For 162.5mAh/g, 142.2mAh/g, 135.7mAh/g and 128.5mAh/g, efficiency is 99.5%, 99.1%, 98.6% first
With 98.9%.After circulation in 50 weeks, its specific capacity conservation rate is respectively 98.7%, 98.4%, 93.5% and 89.6%, is shown in Table 2-table
4。
Table 1 embodiment 1-6 and the granularity of comparative example, tap density, compacted density and specific surface area test result
Table 2 embodiment 1-6 and the specific capacity test result first of comparative example
Table 3 embodiment 1-6 and the efficiency test result first of comparative example
Table 4 embodiment 1-6 and 50 weeks capability retention test results of comparative example
Claims (10)
1. a lithium titanate composite negative electrode materials used by lithium ion batteries, it is characterised in that: described lithium ion battery lithium titanate is multiple
Conjunction negative material, with lithium titanate as matrix, is coated with nanometer ferrous disulfide FeS at matrix2, nanometer curing iron is matrix
The 0.1～10.0% of quality, the granularity of described lithium titanate composite negative electrode materials used by lithium ion batteries is 0.5～18 μm；
Above-mentioned lithium titanate composite negative electrode materials used by lithium ion batteries uses following preparation method to obtain, and comprises the following steps:
Step one, prepare high-purity nm ferrous disulfide, by the elemental mole ratios of composition ferrous disulfide, be 2.0～10.0 μ in granularity
The iron powder of m and purity be 99.9～99.99% sulfur powder in, add account for ferrous disulfide quality 0.1～the sodium chloride of 5.0%, right
The compound of iron powder, sulfur powder and sodium chloride carries out high-energy ball milling, and mill is situated between, the mass ratio of compound is 5～10:1, and rotating speed is 200
～500r/min, ball milling 24～72h, obtain ferrous disulfide material system；With hydrogen peroxide and sodium borohydride in mass ratio 0.2～
1.0:1 forms composite detergent, and composite detergent concentration of polymer solution is 5.0～35.0%, and ferrous disulfide material system is with multiple
Closing detergent solution mass ratio is 0.1～1.0:1, after soaking ferrous disulfide material system 1.0～2.5h, and washing, filter 23～5
Secondary, directly dry at 120～200 DEG C, obtain the high-purity nm ferrous disulfide that granularity is 20.0～50.0nm；
Step 2, mixing, by lithium, the mol ratio 0.7～1.0:1 of titanium, by the lithium source that granularity is 0.5～2.0 μm, granularity is 0.2
～2.5 titanium sources of μm, account for lithium source and titanium source gross mass 0.1～the high-purity nm ferrous disulfide of 10.0%, join containing dispersion
In the aqueous solution of agent and bonding agent, in aqueous solution, dispersant mass content is 1.0～25.0%, and binding agent mass content is 0.1
～5.0%, lithium source and titanium source gross mass are 1:0.6～3.2 with the mass ratio of aqueous solution, zirconia ball with mix after the quality expected
Ratio is 5～10:1, and rotating speed is 200～500r/min, ball milling 0.5～24h, obtains nanoscale and/or the other ball milling of submicron order
Slurry；Described dispersant is more than one in dehydrated alcohol, ethylene glycol and glycerol；Described binding agent is carboxymethyl cellulose
More than one in sodium, butadiene-styrene rubber suspension and politef；Described lithium source is lithium carbonate, Lithium hydrate, lithium nitrate, vinegar
Acid lithium and Lithium Citrate de in more than one；Described titanium source is anatase titanium dioxide, rutile titanium dioxide, barium metatitanate
With more than one in titanium tetraisopropylate；
Step 3, sintering, be dried to obtain dry powder presoma, is 0.6～1.2m at flow3/h.M3Protective gas atmosphere under,
With the programming rate of 0.8～10.0 DEG C/min to 200～300 DEG C, presintering processes 2～5h, then with 0.5～10.0 DEG C/min
Programming rate to 600～800 DEG C, high temperature sintering processes after 2～25h, is naturally cooling to room temperature, obtains lithium ion battery in stove
Use lithium titanate composite anode material.
2. a preparation method for lithium titanate composite negative electrode materials used by lithium ion batteries, comprises the following steps:
Step one, prepare high-purity nm ferrous disulfide, by the elemental mole ratios of composition ferrous disulfide, be 2.0～10.0 μ in granularity
The iron powder of m and purity be 99.9～99.99% sulfur powder in, add account for ferrous disulfide quality 0.1～the sodium chloride of 5.0%, right
The compound of iron powder, sulfur powder and sodium chloride carries out high-energy ball milling, and mill is situated between, the mass ratio of compound is 5～10:1, and rotating speed is 200
～500r/min, ball milling 24～72h, obtain ferrous disulfide material system；With hydrogen peroxide and sodium borohydride in mass ratio 0.2～
1.0:1 forms composite detergent, and composite detergent concentration of polymer solution is 5.0～35.0%, and ferrous disulfide material system is with multiple
Closing detergent solution mass ratio is 0.1～1.0:1, after soaking ferrous disulfide material system 1.0～2.5h, and washing, filter 23～5
Secondary, directly dry at 120～200 DEG C, obtain the high-purity nm ferrous disulfide that granularity is 20.0～50.0nm；
Step 2, mixing, by lithium, the mol ratio 0.7～1.0:1 of titanium, by the lithium source that granularity is 0.5～2.0 μm, granularity is 0.2
～2.5 titanium sources of μm, account for lithium source and titanium source gross mass 0.1～the high-purity nm ferrous disulfide of 10.0%, join containing dispersion
In the aqueous solution of agent and bonding agent, in aqueous solution, dispersant mass content is 1.0～25.0%, and binding agent mass content is 0.1
～5.0%, lithium source and titanium source gross mass are 1:0.6～3.2 with the mass ratio of aqueous solution, zirconia ball with mix after the quality expected
Ratio is 5～10:1, and rotating speed is 200～500r/min, ball milling 0.5～24h, obtains nanoscale and/or the other ball milling of submicron order
Slurry；Described dispersant is more than one in dehydrated alcohol, ethylene glycol and glycerol；Described binding agent is carboxymethyl cellulose
More than one in sodium, butadiene-styrene rubber suspension and politef；Described lithium source is lithium carbonate, Lithium hydrate, lithium nitrate, vinegar
Acid lithium and Lithium Citrate de in more than one；Described titanium source is anatase titanium dioxide, rutile titanium dioxide, barium metatitanate
With more than one in titanium tetraisopropylate；
Step 3, sintering, be dried to obtain dry powder presoma, is 0.6～1.2m at flow3/h.M3Protective gas atmosphere under,
With the programming rate of 0.8～10.0 DEG C/min to 200～300 DEG C, presintering processes 2～5h, then with 0.5～10.0 DEG C/min
Programming rate to 600～800 DEG C, high temperature sintering processes after 2～25h, is naturally cooling to room temperature, obtains lithium ion battery in stove
Use lithium titanate composite anode material.
The preparation method of lithium titanate composite negative electrode materials used by lithium ion batteries the most according to claim 2, it is characterised in that:
Also pulverize after described step 3 sintering, obtain the lithium ion battery lithium titanate composite negative pole that granularity is 0.3～20.0 μm
Material.
The preparation method of lithium titanate composite negative electrode materials used by lithium ion batteries the most according to claim 3, it is characterised in that:
After described pulverizing, the speed of mainshaft is 700～1300r/min, the material jolt ramming after pulverizing is processed 1.0～6.0h, obtains granularity
It it is the lithium titanate composite negative electrode materials used by lithium ion batteries of 0.5～18 μm.
The preparation method of lithium titanate composite negative electrode materials used by lithium ion batteries the most according to claim 4, it is characterised in that:
Described jolt ramming processes and uses mechanical fusion machine.
The preparation method of lithium titanate composite negative electrode materials used by lithium ion batteries the most according to claim 2, it is characterised in that:
The high-energy ball milling of described step one, mill is situated between and uses the zirconia ball of diameter of phi 0.5～Φ 5.0mm.
The preparation method of lithium titanate composite negative electrode materials used by lithium ion batteries the most according to claim 2, it is characterised in that:
The ferrous disulfide material system that the immersion of described step one is used is 0.125～0.87 with composite detergent solution quality ratio:
1。
The preparation method of lithium titanate composite negative electrode materials used by lithium ion batteries the most according to claim 2, it is characterised in that:
Zirconia ball used by the ball milling of described step 2 uses the zirconia ball of diameter of phi 0.5～Φ 5.0mm.
The preparation method of lithium titanate composite negative electrode materials used by lithium ion batteries the most according to claim 2, it is characterised in that:
The protective gas that the sintering of described step 3 is used is more than one in nitrogen, argon and helium.
The preparation method of lithium titanate composite negative electrode materials used by lithium ion batteries the most according to claim 3, its feature exists
In: the pulverizing of described step 3 uses jet mill, is 0.8～1.5MPa in pressure limit, and frequency is 130～190Hz.
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