CN105374991B - Lithium metal-skeleton carbon composite material and preparation method, cathode and secondary cell - Google Patents
Lithium metal-skeleton carbon composite material and preparation method, cathode and secondary cell Download PDFInfo
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- CN105374991B CN105374991B CN201410395114.0A CN201410395114A CN105374991B CN 105374991 B CN105374991 B CN 105374991B CN 201410395114 A CN201410395114 A CN 201410395114A CN 105374991 B CN105374991 B CN 105374991B
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Abstract
This application discloses a kind of lithium metal-skeleton carbon composite preparation methods, and the lithium metal of molten condition is uniformly mixed with porous carbon material carrier, cooling to obtain lithium metal-skeleton carbon composite.Disclosed herein as well is a kind of lithium metal-skeleton carbon composite, secondary battery negative pole, secondary cell and a kind of metal-skeleton carbon composites.The present invention, which prepares lithium metal-skeleton carbon composite, to improve the full property of battery with the formation of dendrite inhibition, and provides higher specific capacity and good cycle performance.
Description
Technical field
The application belongs to energy battery field, more particularly to a kind of lithium metal-skeleton carbon composite and its preparation side
Method, cathode and secondary cell.
Background technique
Lithium battery has high-energy density, good circulation performance, advantages of environment protection, in traffic, communication, electronic equipment
It is used widely in equal fields.
Currently used lithium battery is mainly lithium ion battery, working principle be lithium ion deviate from positive and negative pole material and
It clamps into using graphite as cathode, not high behave always of the capacity of graphite cathode denounces, charging commercial lithium ion battery
Journey lithium ion is deviate from from anode, is embedded in cathode, and lithium ion is deviate from from cathode when electric discharge, insertion anode, in lithium ion from positive and negative anodes
Along with the formation of positive and negative pole surface SEI film during abjection and insertion, active lithium-ion in positive electrode is lost, reduces electricity
The coulombic efficiency in pond leads to the capacity attenuation of battery.Although the generation of this tunic is to have certain benefit for the cyclicity of battery
Place, but the capacity of positive electrode is generally bigger than the capacity of graphite cathode by 10% ~ 15% in the lithium ion battery used, makes up
The loss of positive lithium ion.
Using lithium metal as negative electrode material, it is capable of providing sufficient lithium ion, avoids the lithium loss of positive electrode, energy
The energy density of battery is enough improved, while can be improved the operating voltage of battery, this battery using lithium metal as cathode
Commonly referred to as lithium battery.When using lithium metal as battery cathode, during the charging process, lithium ion sinks on lithium anode
Product forms dendrite, causes diaphragm to pierce through short circuit, overheat, electrolyte decomposition is caused even to burn, and causes battery dangerous, so not having
It is continued to use.FMC Corp., the U.S. (patent US 8,021,496 B2, US 2013/0181160 A1, CN
102255080 A) using melting emulsification method prepare lithium metal particle, its surface is modified again later, is stablized
Existing lithium metal particle, is prepared into electrode slice as battery cathode for this material and uses.South Korea's Woo Young Yoon project
Group, (bibliography Adv. Funct. Mater. 2013,23,1019-1027, Journal of Power Sources
2010,195,6143-6147.) the same method using melting emulsification prepares lithium metal particle, in lithium metal particle surface
It is modified, tabletting prepares electrode later.Chinese Tianjin China Energy Lithium Co., Ltd. (patent CN 102122709A) will prepare
In good lithium metal particle electrode pressing, the cathode containing lithium is obtained, the loss of lithium in anode material for lithium-ion batteries is made up.It adopts
Lithium metal particle is prepared with the method for melting emulsification, such method needs violent stirring (> 10000rpm), emulsification end
Afterwards, multiple washing is needed, complex steps, preparation process is harsher for equipment requirement.
Summary of the invention
The purpose of the present invention is to provide a kind of lithium metal-skeleton carbon composite material and preparation methods, cathode and secondary
Battery, to overcome deficiency in the prior art.
To achieve the above object, the invention provides the following technical scheme:
The embodiment of the present application discloses a kind of lithium metal-skeleton carbon composite, including porous carbon material carrier and
The lithium metal being formed in the carbon material carrier hole.
Preferably, in above-mentioned lithium metal-skeleton carbon composite, the carbon material is carbon fiber microballoon, carbon nanometer
Pipe microballoon or acetylene black.
Preferably, in above-mentioned lithium metal-skeleton carbon composite, the average pore size of the carbon nanotube microballoon is 10
~50nm。
Preferably, in above-mentioned lithium metal-skeleton carbon composite, the average diameter of the carbon nanotube microballoon is 1 μ
M ~ 100 μm, the carbon nanotube microballoon conductivity are 1*10-3~10S.cm-1, pressure model that the carbon nanotube microballoon can be born
It encloses for 0 ~ 20MPa, the carbon nanotube microballoon specific surface area is 100 ~ 1500m2/ g, the carbon nanotube microballoon at least have micro-
Coccoid entity aggregates structure, spherical aggregated structure, spherical aggregated structure, porous spherical aggregated structure and the aggregation of bagel shape
Any one in structure.
The embodiment of the present application also discloses a kind of using above-mentioned lithium metal-skeleton carbon composite secondary battery negative pole.
Correspondingly, disclosed herein as well is a kind of secondary cells comprising above-mentioned cathode.
Preferably, in above-mentioned secondary cell, the secondary cell is lithium metal-oxide cell, lithium metal-polymerization
Object battery or rechargeable lithium ion batteries.
The embodiment of the present application also discloses a kind of preparation method of lithium metal-skeleton carbon composite, by molten condition
Lithium metal is uniformly mixed with porous carbon material carrier, cooling to obtain lithium metal-skeleton carbon composite.
Preferably, in above-mentioned lithium metal-skeleton carbon composite preparation method, the carbon material carrier is received for carbon
Mitron microballoon, the preparation method of the carbon nanotube microballoon include: at least to be dispersed in carbon nanotube to be formed in solvent to be free of
It is spray-dried after the dispersion liquid of surfactant, so that the carbon nanotube microballoon be made.
Preferably, in above-mentioned lithium metal-skeleton carbon composite preparation method, the condition packet of the spray drying
Include: inlet air temperature is 150 ~ 250 DEG C, and leaving air temp is 75 ~ 150 DEG C, and spray velocity is 1 ml/hour to 10 ton/hours.
Compared with the prior art, the advantages of the present invention are as follows: the lithium metal that the present invention prepares-skeleton carbon composite can
To be applied to miscellaneous lithium battery, lithium metal-oxide cell, lithium metal-polymer battery, chargeable lithium can be applied to
Ion battery.A noticeable field is rechargeable lithium ion batteries in portable electronic device and hybrid power vapour
The application of vehicle provides highest specific capacity and good in these applications it is desirable to serondary lithium battery and guarantee under safety in advance
Good cycle performance, and lithium metal is as optimal negative electrode material, due to generating dendrite, the low difference of safety in charge and discharge process
So cannot directly use, the present invention, which prepares lithium metal-skeleton carbon composite, to improve battery with the formation of dendrite inhibition
Full property, and provide higher specific capacity and good cycle performance.
Detailed description of the invention
In order to illustrate the technical solutions in the embodiments of the present application or in the prior art more clearly, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The some embodiments recorded in application, for those of ordinary skill in the art, without creative efforts,
It is also possible to obtain other drawings based on these drawings.
Fig. 1 show the electricity that lithium metal obtained in the embodiment of the present invention 2-acetylene black composite material and LiFePO4 are constituted
Pond charge-discharge performance figure；
Fig. 2 show the lithium metal carbon nanotube microballoon composite material scanning electron microscope (SEM) photograph prepared in the embodiment of the present invention 3,
The amplification factor of left figure is 500 times, and right figure is 10000 times；
Fig. 3 show the x-ray powder of lithium metal carbon nanotube microsphere compound electrode obtained in the embodiment of the present invention 4
Diffraction pattern；
The amplification factor of the stereoscan photograph left figure of carbon nanotube microballoon obtained in the embodiment of the present invention 5 shown in Fig. 4
It is 500 times, right figure is 10000 times；
Fig. 5 show lithium metal carbon nanotube microballoon composite material obtained in the embodiment of the present invention 5 and metal lithium sheet structure
At battery, the battery is in 0.2mA constant-current charge (current density 0.1mA/cm2) time that dendrite causes short circuit is tested, comparison
Experiment is lithium metal and the battery that metal lithium sheet is constituted；
Fig. 6 show lithium metal carbon nano tube compound material obtained in the embodiment of the present invention 5 as cathode, and LiMn2O4 is made
For the simulated battery charge-discharge performance figure of the LiMn2O4 composition of anode；
Lithium metal obtained in the embodiment of the present invention 5 shown in Fig. 7-carbon nanotube microballoon composite material and LiFePO4 are constituted
Battery charging and discharging cycle performance figure.
Specific embodiment
The embodiment of the present application discloses a kind of lithium metal-skeleton carbon composite, including porous carbon material carrier and
The lithium metal being formed in the carbon material carrier hole.
Above-mentioned carbon material skeleton structure can be with carbon fiber, microballoon (the average hole of the materials such as carbon nanotube carbon composition
Diameter 10-50nm) structure, acetylene black (average pore size 14.4nm) also can be used.Average pore size can also be selected in 10-
Carbon skeleton material within the scope of 100nm is as the carrier for absorbing molten metal lithium.
Preferably, the microballoon that carbon material skeleton is prepared using carbon nanotube by spray drying, it is main
The spherical shape or near-spherical particle be made of carbon nanotube, spherical or near-spherical particle the average diameter is 1 μm~100 μm,
Preferably 1 μm~25 μm；Carbon nanotube micro-sphere material can have tiny spherical solid aggregated structure, spherical aggregated structure, class ball
Any one in shape aggregated structure, porous spherical aggregated structure and bagel shape aggregated structure, but not limited to this；Carbon nanotube
It may be selected from but not limited to the group of any one or more in multi-walled carbon nanotube, double-walled carbon nano-tube and single-walled carbon nanotube
It closes；Carbon nanotube may be selected from but not limited to untreated pure commodity carbon nano tube, the purifying carbon nano-tube without catalyst
It is surface-functionalized for aforementioned process with the combination of any one or more in the carbon nanotube Jing Guo surface-functionalized processing
The carbon nanotube of processing, wherein the group modified in carbon nano tube surface may be selected from but not limited to-COOH ,-OH ,-NH2Equal bases
Group；The carbon nanotube system uses the pure carbon nanotube without catalyst, the especially pure multi wall carbon without catalyst to receive
Mitron.
Further, surface, foregoing carbon nanotubes microballoon conductivity are 1*10 after tested-3~10S.cm-1, preferably 2*10-3~0.1S.cm-1。
Further, by receiving pressure test to the carbon nanotube microballoon, it can be found that its allowable stress range
For 0 ~ 20MPa, and after 20MPa pressure test, still sphere is kept not rupture.
Further, by carrying out specific surface area test to the carbon nanotube microballoon, it can be found that its specific surface area is
100~1500m2/ g, preferably 150 ~ 500m2/g。
Another aspect provides a kind of preparation methods of carbon nanotube microballoon for the embodiment of the present application, comprising: at least by carbon
Nanotube be dispersed in solvent formed without surfactant dispersion liquid after be spray-dried, so that the carbon nanometer be made
Pipe microballoon.
The form of the carbon nanotube micro-sphere material can be powdered or particle.
More specifically, as one of viable solution of the invention, which may include: at least to receive carbon
Mitron dispersion obtains the dispersion liquid for being free of surfactant in a solvent, then by the atomizer of dispersion liquid input spray dryer
In, and small misty liquid droplets are formed, and make the misty liquid droplets with thermal current parallel flow contact, in the spray dryer
Solvent in the liquid droplet evaporates rapidly, so assemble the carbon nanotube in the liquid droplet to form carbon nanotube micro-
The carbon nanotube microballoon is discharged from the drying tower bottom and/or cyclone separator of the spray dryer thereafter for ball.
In an exemplary embodiments, which be may include steps of:
A, carbon nanotube is distributed in dispersing agent (without surfactant), obtains carbon nano tube dispersion liquid；
B, dispersion liquid will be obtained in step A to spray with certain speed by the nozzle of spray dryer, it is presetting enter wind-warm syndrome
Degree and leaving air temp, it is stirring that solution is kept in spray process, depending on different model spray dryer and adjust fluid injection speed
Degree；
C, natural cooling, that is, carbon nanotube microballoon needed for obtaining.
Preferably, it is 150 ~ 250 DEG C that the condition of aforementioned spray drying, which includes: inlet air temperature, and leaving air temp is 75 ~ 150 DEG C；
Spray drying condition particularly preferably includes: that inlet air temperature is 190 ~ 210 DEG C, and leaving air temp is 90 ~ 110 DEG C.
Further, the condition of spray drying may preferably further comprise: spray velocity is 1 ml/hour~10 ton/hours,
It is specifically adjusted according to the difference of spray dryer model and specification.
Preferably, aforementioned carbon nanometer can be selected from common carbon nanotube, carboxylic carbon nano-tube, hydroxyl carbon nano tube, ammonia
Base carbon nano tube etc., and its purity is pure not less than chemistry.
Preferably, the dispersion liquid includes the carbon nanotube that concentration is 10 ~ 50g/L, it is further preferred that dispersion liquid includes
Concentration is 10 ~ 15g/L.
Further, the organic and/or inorganic liquid that aforementioned solvents use can make carbon nanotube evenly dispersed, for example,
It is preferred that the combination of any one or more of water, ammonium hydroxide, hydrochloric acid solution, ethyl alcohol, acetone, isopropanol.
And be more specifically preferably implemented in case one, the solvent can be the ethyl alcohol and water that volume ratio is 1:10
Mixture.
The embodiment of the present application also discloses a kind of preparation method of lithium metal-skeleton carbon composite, by molten condition
Lithium metal is uniformly mixed with porous carbon material carrier, cooling to obtain lithium metal-skeleton carbon composite.
Above-mentioned lithium metal-skeleton carbon composite preparation method specifically includes:
The first step is chosen, prepares framework carbon material, chooses the porous carbon materials of different pore size as the load for absorbing lithium metal
Body, wherein it is preferred that porous carbon materials of the aperture within the scope of 10-100nm.
Wherein the preparation of porous carbon materials is optimal with the carbon nanotube microballoon that spray drying process is prepared.
Second step weighs a certain proportion of metal lithium sheet (LITHIUM BATTERY) and framework carbon material.
Third step, by the two be uniformly mixed be placed in full of argon gas in the inert heater of lithium.
4th step, heating response device heat lithium metal fusing point or more.
5th step is stirred in lithium metal reflow process.
6th step is reduced to room temperature after mixing, obtains lithium metal-skeleton carbon composite.
After heating melts lithium metal, framework carbon material is absorbed into the hole of framework carbon material, equally may be used
Low-melting-point metals such as sodium, potassium, tin are absorbed into carbon material skeleton according to this.
To make the object, technical solutions and advantages of the present invention clearer, with reference to the accompanying drawing to specific reality of the invention
The mode of applying is described in detail.The example of these preferred embodiments is illustrated in the accompanying drawings.Shown in attached drawing and according to
The embodiments of the present invention of attached drawing description are only exemplary, and the present invention is not limited to these embodiments.
Here, it should also be noted that, in order to avoid having obscured the present invention because of unnecessary details, in the accompanying drawings only
Show with closely related structure and/or processing step according to the solution of the present invention, and be omitted little with relationship of the present invention
Other details.
Embodiment 1
200mg Battery grade lithium metal is weighed first with 200mg commercialization porous carbon (average pore size 2.6nm) jointly as right
In the inert heater of lithium metal, it is heated to the temperature of lithium metal fusing, is vigorously stirred, last for several minutes, is sent out in mixed process
Existing porous carbon cannot function as carrier absorption molten metal lithium, is formed by compound into bulk, illustrates that average pore size is too small, no
Molten metal lithium can effectively be absorbed.
Embodiment 2
Weigh first the acetylene black (average pore size 14.4nm) of 200mg Battery grade lithium metal and 200mg commercialization jointly as
It to the temperature in the inert heater of lithium metal, being heated to lithium metal fusing, is vigorously stirred, continues 6-8 minutes, mixing end
Afterwards, it is cooled to room temperature, whole process carries out in argon atmosphere.
Lithium metal-acetylene black microballoon is obtained, wherein the load capacity of lithium metal are as follows: 8.0%.
Use material obtained above as the cathode of lithium battery:
Anode material for lithium-ion batteries is LiFePO4: PVFD:AB=88:5:7, with a thickness of 150um, electrolyte 1mol/L
LiPF6/ EC-DMC (1:1 vol), is assembled into button cell (CR 2025), recycles 25 times, the library of battery in entire cyclic process
Human relations are inefficient, and as the cycle progresses, coulombic efficiency tends towards stability.Fig. 1 is circulation 25 times charge-discharge performances of the battery
Schematic diagram.
Embodiment 3
The preparation of carbon nanotube microballoon: 200ml is added without any chemically treated multi-walled carbon nanotube in 2g first and is gone
Ionized water, it is rear that 20mL dehydrated alcohol is added.Sealing stirring, 130W ultrasonic probe are ultrasonically treated 5h, keep sample evenly dispersed.It finishes
Spray dryer is added in sample afterwards.Inlet air temperature is set as 200 DEG C, and leaving air temp is set in 150 DEG C, and atomisation pressure is set as
40MPa, sample volume are set as 500mL/h, obtain carbon nanotube micro-sphere material after dry.Nitrogen adsorption desorption is carried out to microballoon
Test, microballoon specific surface area are 151m2/ g, average pore size 18.7nm.
Weighing 100mg Battery grade lithium metal and 100mg carbon nanotube microballoon first, (carbon nanotube is obtained by spray drying
, average pore size is 18.7 nm) as (molten higher than lithium metal in the inert heater of lithium metal, being heated to 220 DEG C
Point), stirring continues 6 minutes, mixing terminates, and is cooled to room temperature, and whole process carries out in argon atmosphere.
Lithium metal-carbon nanotube microballoon composite material is obtained, wherein the mass percentage of lithium metal are as follows: 15.0%.
Fig. 2 shows the lithium metal carbon nanotube microballoon composite material scanning electron microscope (SEM) photograph prepared, it can be seen for preparing
Material be micron spherical structure.
Embodiment 4
The preparation of carbon nanotube microballoon: 200ml is added without any chemically treated multi-walled carbon nanotube in 3g first and is gone
Ionized water, it is rear that 20mL dehydrated alcohol is added.Sealing stirring, 130W ultrasonic probe are ultrasonically treated 10h, keep sample evenly dispersed.It is complete
Spray dryer is added in sample after finishing.Inlet air temperature is set as 200 DEG C, and leaving air temp is set in 120 DEG C, atomisation pressure setting
For 40MPa, sample volume is set as 500mL/h, obtains carbon nanotube micro-sphere material after dry.It is de- that nitrogen adsorption is carried out to microballoon
Attached test, microballoon specific surface area are 197m2/ g, average pore size 22.9nm.
Weighing 100mg Battery grade lithium metal and 100mg carbon nanotube microballoon first, (carbon nanotube is obtained by spray drying
, average pore size 22.9nm) as in the inert heater of lithium metal, being heated to 220 DEG C (higher than fusing points of lithium metal),
Stirring, continues 6 minutes, mixing terminates, and is cooled to room temperature, and whole process carries out in argon atmosphere.
Lithium metal-carbon nanotube microballoon composite material is obtained, wherein the mass percentage of lithium metal are as follows: 35.0%.
Lithium metal-carbon nanotube microballoon composite material XRD diagram of Fig. 3 display preparation, it can be seen that in the material of preparation
Containing lithium metal, simultaneously because being partially oxidized in XRD characterization process material, while the characteristic peak of lithium hydroxide is shown.
Embodiment 5
The preparation of carbon nanotube microballoon: 200ml is added without any chemically treated multi-walled carbon nanotube in 4g first and is gone
Ionized water, it is rear that 20mL dehydrated alcohol is added.Sealing stirring, 130W ultrasonic probe are ultrasonically treated 10h, keep sample evenly dispersed.It is complete
Spray dryer is added in sample after finishing.Inlet air temperature is set as 200 DEG C, and leaving air temp is set in 150 DEG C, atomisation pressure setting
For 40MPa, sample volume is set as 500mL/h, obtains carbon nanotube micro-sphere material after dry.It is de- that nitrogen adsorption is carried out to microballoon
Attached test, microballoon specific surface area are 254m2/ g, average pore size 31.4nm.
Fig. 4 shows the stereoscan photograph for the carbon nanotube microballoon that spray drying is prepared.
Weighing 200mg Battery grade lithium metal and 200mg carbon nanotube microballoon first, (carbon nanotube is obtained by spray drying
, average pore size is placed in (molten higher than lithium metal in the inert heater of lithium metal, being heated to 220 DEG C for 31.4 nm)
Point), stirring continues 6 minutes, mixing terminates, and is cooled to room temperature, and whole process carries out in argon atmosphere.
Lithium metal-carbon nanotube microballoon composite material is obtained, wherein the mass percentage of lithium metal are as follows: 43.0%.
Fig. 5 shows lithium metal and lithium metal carbon nanotube microballoon hybrid electrode as the total electrode of work respectively and metal lithium sheet
The half-cell of composition studies the formation time of dendrite later by the lithium platingactive in metal lithium sheet to working electrode, can be with from figure
Find out in the close 0.1mA/cm of same electric current2Under the conditions of degree, according to Sand ' time formula it is found that lithium metal carbon nanotube microballoon
Hybrid electrode is due to the big specific surface area of itself, and active electrode current density becomes very little, when can extend the formation of dendrite
Between, so all generated without dendrite after 350 hours, and the specific surface area of metal lithium sheet is much smaller, in 60 hours or so shapes
At dendrite, the short circuit of battery is caused.
Use material obtained above as the cathode of lithium battery:
Anode material for lithium-ion batteries is LiMnO4:PVFD:AB=88:5:7, with a thickness of 150um, electrolyte 1mol/L
LiPF6/EC-DMC (1:1 vol), is assembled into button cell (CR 2025), using 1C current charging and discharging, recycles 100 times, battery
Capacity is almost without loss.The charge-discharge performance schematic diagram that Fig. 6 is the circulating battery 100 times.
Anode material for lithium-ion batteries is LiFePO4:PVFD:AB=88:5:7, with a thickness of 150um, electrolyte 1mol/L
LiPF6/EC-DMC (1:1 vol), is assembled into button cell (CR 2025), recycles 30 times, the specific capacity of battery is almost without damage
It loses.Fig. 7 is circulation 30 times charge-discharge performance schematic diagrames of the battery.
Fig. 6 is the charge-discharge performance figure of lithium manganate battery, is recycled 100 times, specific capacity is not lost substantially.
Fig. 7 is the charge-discharge performance figure of phosphoric acid acid lithium battery, is recycled 25 times, coulombic efficiency is maintained at 100%, specific volume
Amount is not lost substantially.
Embodiment 6
200mg Battery grade lithium metal is weighed first and 200mg commodity XE-2 carbon material (10 nm of average pore size) is common extremely
In to the inert heater of lithium metal, it is heated to the temperature of lithium metal fusing, is vigorously stirred, continues 6-8 minutes, mixing terminates
Later, it is cooled to room temperature, whole process carries out in argon atmosphere.
Lithium metal-acetylene black microballoon is obtained, wherein the load capacity of lithium metal are as follows: 5.0%.
Finally, it is to be noted that, the terms "include", "comprise" or its any other variant be intended to it is non-exclusive
Property include so that include a series of elements process, method, article or equipment not only include those elements, but also
Further include other elements that are not explicitly listed, or further include for this process, method, article or equipment it is intrinsic
Element.
Claims (11)
1. a kind of lithium metal-carbon nanotube microballoon composite material, which is characterized in that the lithium metal-carbon nanotube microballoon is compound
Material has micron spherical structure, including the carbon nanotube microballoon as porous carbon material carrier and is formed in the carbon and receives
Lithium metal in the hole of mitron microballoon, wherein the average diameter of the carbon nanotube microballoon is 1 μm~100 μm, is had average
Aperture is the hole of 10~100nm, and the lithium metal is complementary with the pore shape of the carbon nanotube microballoon.
2. lithium metal according to claim 1-carbon nanotube microballoon composite material, it is characterised in that: the carbon nanotube
Microballoon is the spherical shape being made of carbon nanotube or near-spherical particle, is formed in solvent by the way that carbon nanotube to be dispersed in
Equal phase dispersant liquid is spray-dried and is prepared.
3. lithium metal according to claim 2-carbon nanotube microballoon composite material, it is characterised in that: the carbon nanotube
The average pore size of microballoon is 10~50nm.
4. lithium metal according to claim 3-carbon nanotube microballoon composite material, it is characterised in that: the carbon nanotube
Microballoon conductivity is 1*10-3~10Scm-1, the pressure limit that the carbon nanotube microballoon can be born is 0~20MPa, described
Carbon nanotube microballoon specific surface area is 100~1500m2/ g, the carbon nanotube microballoon at least have tiny spherical solid aggregation
Any one in structure, spherical aggregated structure, spherical aggregated structure and bagel shape aggregated structure.
5. a kind of secondary battery negative pole, it is characterised in that: the negative electrode material is any lithium metal-carbon of Claims 1-4
Nanotube microballoon composite material.
6. a kind of secondary cell, it is characterised in that: including the cathode described in claim 5.
7. secondary cell according to claim 6, it is characterised in that: the secondary cell is rechargeable lithium ion batteries.
8. secondary cell according to claim 6, it is characterised in that: the secondary cell is lithium metal-oxide cell
Or lithium metal-polymer battery.
9. a kind of be used to prepare lithium metal according to any one of claims 1 to 4-carbon nanotube microballoon composite material side
Method, it is characterised in that: the lithium metal of molten condition and carbon nanotube microballoon are mixed directly, it is cooling to obtain lithium metal-carbon
Nanotube microballoon composite material, wherein the average diameter of the carbon nanotube microballoon be 1 μm~100 μm, be with average pore size
The hole of 10~100nm.
10. lithium metal according to claim 9-carbon nanotube microballoon composite material preparation method, it is characterised in that: institute
The preparation method for stating carbon nanotube microballoon includes: to be dispersed in carbon nanotube to be formed in solvent to be free of the equal of surfactant
Phase dispersant liquid forms small misty liquid droplets, and make then by the atomizer of the equal phase dispersant liquid input spray dryer
The misty liquid droplets, with thermal current parallel flow contact, steam the solvent in the misty liquid droplets rapidly in the spray dryer
Hair, and then the carbon nanotube in the misty liquid droplets is made to assemble to form carbon nanotube microballoon, thereafter by the carbon nanotube microballoon
It is discharged from the spray dryer.
11. lithium metal according to claim 10-carbon nanotube microballoon composite material preparation method, it is characterised in that:
The condition of the spray drying includes: that inlet air temperature is 150~250 DEG C, and leaving air temp is 75~150 DEG C, and spray velocity is 1 milli
L/h to 10 ton/hours.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410395114.0A CN105374991B (en) | 2014-08-13 | 2014-08-13 | Lithium metal-skeleton carbon composite material and preparation method, cathode and secondary cell |
| KR1020167029453A KR101900780B1 (en) | 2014-03-21 | 2015-03-20 | Porous carbon nanotube microsphere and preparation method therefor and application thereof, lithium metal-skeleton carbon composite material and preparation method therefor, negative electrode, and battery |
| PCT/CN2015/074733 WO2015139660A1 (en) | 2014-03-21 | 2015-03-20 | Porous carbon nanotube microsphere and preparation method therefor and application thereof, lithium metal-skeleton carbon composite material and preparation method therefor, negative electrode, and battery |
| JP2016558783A JP6445585B2 (en) | 2014-03-21 | 2015-03-20 | Porous carbon nanotube microspheres and production method and use thereof, metallic lithium-skeleton carbon composite material and production method thereof, negative electrode, and battery |
| EP15765300.7A EP3133047B8 (en) | 2014-03-21 | 2015-03-20 | Lithium metal-skeleton carbon composite and preparation method therefor, negative electrode, and battery |
| US15/127,809 US10868298B2 (en) | 2014-03-21 | 2015-03-20 | Porous carbon nanotube microsphere and preparation method and use thereof, lithium metal-skeleton carbon composite and preparation method thereof, negative electrode, and battery |
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| CN201410395114.0A CN105374991B (en) | 2014-08-13 | 2014-08-13 | Lithium metal-skeleton carbon composite material and preparation method, cathode and secondary cell |
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| EP3913706A4 (en) * | 2020-03-30 | 2022-03-16 | China Energy Cas Technology Co., Ltd. | Pre-lithiated negative electrode and preparation method therefor, and lithium ion battery and supercapacitor having pre-lithiated negative electrode |
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|---|---|---|---|---|
| CN107305941B (en) * | 2016-04-21 | 2019-12-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | Lithium-carbon composite material, preparation method and application thereof, and lithium compensation method |
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| CN112447410B (en) * | 2019-09-03 | 2022-05-06 | 黑龙江大学 | Preparation method of lithium iron phosphate/carbon nanotube microsphere positive electrode material, positive electrode material and optimization method of water-based lithium ion capacitor |
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| CN112133901B (en) * | 2020-10-22 | 2021-11-30 | 隆能科技(南通)有限公司 | Lithium-carbon composite material and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110104571A1 (en) * | 2009-11-02 | 2011-05-05 | Aruna Zhamu | Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries |
| CN103384000A (en) * | 2012-05-02 | 2013-11-06 | 现代自动车株式会社 | Lithium electrode for lithium metal battery and method of manufacturing the lithium electrode |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5495887B2 (en) * | 2009-04-28 | 2014-05-21 | 株式会社デンソー | Negative electrode for non-aqueous electrolyte battery and non-aqueous electrolyte battery |
| WO2011154869A2 (en) * | 2010-06-08 | 2011-12-15 | Ramot At Tel-Aviv University Ltd | Rechargeable alkali metal-air battery |
-
2014
- 2014-08-13 CN CN201410395114.0A patent/CN105374991B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110104571A1 (en) * | 2009-11-02 | 2011-05-05 | Aruna Zhamu | Nano-structured anode compositions for lithium metal and lithium metal-air secondary batteries |
| CN103384000A (en) * | 2012-05-02 | 2013-11-06 | 现代自动车株式会社 | Lithium electrode for lithium metal battery and method of manufacturing the lithium electrode |
Non-Patent Citations (1)
| Title |
|---|
| "反相微乳液法合成碳纳米管微球";刘云泉等;《无机材料学报》;20090915;第24卷(第5期);第993-997页 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3913706A4 (en) * | 2020-03-30 | 2022-03-16 | China Energy Cas Technology Co., Ltd. | Pre-lithiated negative electrode and preparation method therefor, and lithium ion battery and supercapacitor having pre-lithiated negative electrode |
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