CN109309197A - Improve the method and its equipment of the yield of lithium carbon composite mass production - Google Patents
Improve the method and its equipment of the yield of lithium carbon composite mass production Download PDFInfo
- Publication number
- CN109309197A CN109309197A CN201710609084.2A CN201710609084A CN109309197A CN 109309197 A CN109309197 A CN 109309197A CN 201710609084 A CN201710609084 A CN 201710609084A CN 109309197 A CN109309197 A CN 109309197A
- Authority
- CN
- China
- Prior art keywords
- lithium
- reaction kettle
- carbon
- carbon nanotube
- carbon composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides the method and its equipment of a kind of yield for improving the mass production of lithium carbon composite.Specifically, the method includes successively carrying out the following steps under an inert atmosphere: (1) being added sequentially to lithium and porous carbon materials carrier in reaction kettle with 3: 1 to 1: 1 weight ratio；(2) reaction kettle is heated to 200-220 DEG C of temperature, and is stirred the mixture in reaction kettle in advance 1-3 minutes with the revolving speed of 70-100 revs/min of blender；(3) reaction kettle is heated to 230-280 DEG C of temperature, and is quickly stirred the mixture in reaction kettle 20-60 minutes with the revolving speed of 300-700 revs/min of blender；(4) stop stirring and being cooled to room temperature reaction kettle, to obtain the lithium carbon composite.According to the technique and scheme of the present invention, can be with high yield mechanization production lithium carbon composite, and obtain the effect for shortening preparation time, the consistency for improving product.
Description
Technical field
The present invention relates to materials science fields, specifically, the present invention provides one kind for improving lithium carbon composite batch
Quantify the method and its equipment of the yield of production.
Background technique
The advantages that specific energy of lithium battery Yin Qigao, the cycle life of length, have been widely used for consumer electronics, electronic vapour
The fields such as vehicle and energy storage.But lithium battery is compound to contain elemental lithium as anode at present, and using graphite as bearing
Pole, and the specific capacity limit of graphite negative electrodes material is about 370mAh/g, has been difficult to further mention based on this negative electrode material
The energy density of high lithium battery, it is difficult to adapt to demand of the market to higher energy density lithium battery.Since lithium anode has
High specific capacity (3860mAh/g), low electrode potential (- 3.04V vs standard hydrogen electrode), the specific energy of lithium battery Yin Qigao,
Long cycle life, high voltage and be widely used in the fields such as consumer electronics, electric car and energy storage.Lithium anode has height
Specific capacity (3860mAh/g), low electrode potential (- 3.04V vs SHE) and small density (0.59g/cm-3) a series of excellent
Gesture can significantly improve the energy density of lithium battery using lithium metal as battery cathode.Lithium metal, can as battery cathode simultaneously
To provide lithium ion, then anode can use the higher material without elemental lithium of capacity, such as sulphur, air.
However, lithium anode battery constantly forms dendrite and " dead lithium " in cyclic process, lead to that coulombic efficiency is low, follows
The ring service life is short.Importantly, the growth of dendrite is possible to that diaphragm can be pierced through and causes positive and negative anodes to connect and internal short-circuit occurs, lead
Cause releases a large amount of heat, and the burning of battery is caused even to explode.The above problem makes lithium anode in the application of recent decades
It is extremely limited.
Increase lithium metal specific surface area and reduce the current density of metallic lithium surface, is that one kind of dendrite inhibition growth has
Effect method.FMC Corp. of the U.S. prepares lithium metal particle using the method for melting emulsification, is modified, is obtained on its surface later
To the lithium metal particle that can be stabilized in dry air, this material can be prepared into electrode slice and use as battery cathode
(referring to 102255080 A of US 8,021,496 B2, US 2013/0181160 A1, CN).But this melting is used to emulsify
The lithium grain diameter that technology prepares is 20-100 microns, and particle size is larger, limited to the raising of electrode specific surface area, and
And the preparation method needs of this melting emulsification are vigorously stirred and repeatedly filter cleaning, step is complicated, and equipment cost is high.South Korea is high
The Woo Young Yoon team of beautiful university prepares lithium metal particle by melting emulsion process, and is surface modified to it,
(referring to Journal of Power Sources, 2010,195 (18): 6143-6147) is grown with dendrite inhibition.Chinese science
Suzhou Nano Technique & Nano Bionic Research Inst. of institute prepares a kind of lithium metal-skeleton carbon composite, by the gold of molten condition
Belong to lithium uniformly to mix with porous carbon material carrier, cooling obtains lithium carbon composite, restrained effectively branch using the material
Crystals growth, improves the safety of battery, and provides higher specific capacity and good cycle performance (referring to PCT international application
Publication number WO 2015139660A1；Chinese Patent Application No. CN 201410395114.0).Although above method is in dendrite inhibition
Growth aspect has remarkable result, but the preparation of above-mentioned lithium metal-skeleton carbon composite is needed still in laboratory level
It is prepared using manual method, it is difficult to produce in enormous quantities.In addition, low according to the obtained product yield of the above method, consistency compared with
Difference.
Therefore, current research can be become in the method that high yield produces lithium carbon composite in batches by developing one kind
One of emphasis.
Summary of the invention
From technical problem described above, the object of the present invention is to provide one kind for producing lithium in batches with high yield
The method of carbon composite, this method can be with high yield mechanization production lithium carbon composite, and obtains shortening preparation
Time, improve product consistency effect.
The present inventor passes through thoroughgoing and painstaking research, completes the present invention.
According to an aspect of the invention, there is provided a kind of method for producing lithium carbon composite in batches, the side
Method includes successively carrying out the following steps under an inert atmosphere:
(1) lithium and porous carbon materials carrier are added sequentially in reaction kettle with 3: 1 to 1: 1 weight ratio；
(2) reaction kettle is heated to 200-220 DEG C of temperature, and will with the revolving speed of 70-100 revs/min of blender
Mixture in reaction kettle stirs 1-3 minutes in advance；
(3) reaction kettle is heated to 230-280 DEG C of temperature, and will with the revolving speed of 300-700 revs/min of blender
Mixture in reaction kettle quickly stirs 20-60 minutes；With
(4) stop stirring and being cooled to room temperature reaction kettle, to obtain the lithium carbon composite.
According to another aspect of the present invention, a kind of method for above-mentioned batch production lithium carbon composite is provided
Equipment, comprising:
Reaction kettle；
Heating and attemperator, the heating and attemperator are for heating the reaction kettle and keeping its temperature；With
Agitating device, the agitating device are used to stir the material in the reaction kettle.
Compared with the prior art in this field, the present invention has the advantages that
1. can be with high yield batch large-scale production lithium carbon composite；With
2. lithium metal-porous carbon composite of different batches production has preferable consistency.
Detailed description of the invention
Fig. 1 shows the various blenders for composite material preparation；
Fig. 2 is shown wherein using the lithium-carbon nanotube microballoon composite material prepared in the embodiment 1 of paddle agitating paddle
Discharge curve；
Fig. 3 is shown wherein using the lithium-carbon nanotube microballoon composite material prepared in the embodiment 1 of paddle agitating paddle
Scanning electron microscope (SEM) photo, wherein the amplification factor of left figure is 1000 times, and the amplification factor of right figure is 18000 times；
Fig. 4, which is shown, wherein to be made using the lithium-carbon nanotube microballoon composite material prepared in the embodiment 1 of paddle agitating paddle
For the constant current perseverance volume test curve of simulated battery manufactured by cathode；
Fig. 5 is shown wherein using the lithium-carbon nanotube microballoon composite material prepared in the embodiment 2 of anchor formula agitating paddle
Discharge curve；
Fig. 6 is shown wherein using the lithium-carbon nanotube microballoon composite material prepared in the embodiment 2 of anchor formula agitating paddle
Scanning electron microscope (SEM) photo, wherein the amplification factor of left figure is 1000 times, and the amplification factor of right figure is 10000 times；
Fig. 7, which is shown, wherein to be made using the lithium-carbon nanotube microballoon composite material prepared in the embodiment 2 of anchor formula agitating paddle
For the constant current perseverance volume test curve of simulated battery manufactured by cathode；
Fig. 8 shows the lithium-carbon fiber microballoon composite material discharge curve prepared in embodiment 3；
Fig. 9 shows that the lithium-carbon fiber microballoon composite material scanning electron microscope (SEM) prepared in embodiment 3 is shone
Piece, wherein the amplification factor of left figure is 1000 times, and the amplification factor of right figure is 10000 times；Know
Figure 10 shows the lithium-carbon fiber microballoon composite material prepared in embodiment 3 as the electricity of simulation manufactured by cathode
The constant current perseverance volume test curve in pond.
Specific embodiment
It should be appreciated that without departing from the scope or spirit of the present disclosure, those skilled in the art can be according to this
The introduction of specification imagines other various embodiments and can modify to it.Therefore, specific embodiment below is not
Restrictive meaning.
Unless otherwise specified, expression characteristic size, quantity and materialization used in specification and claims are special
All numbers of property be construed as to be modified by term " about " in all cases.Therefore, unless there are opposite
Illustrate, the numerical parameter otherwise listed in description above and the appended claims is approximation, those skilled in the art
Member can seek the required characteristic obtained using teachings disclosed herein, suitably change these approximations.With endpoint table
The use for the numberical range shown includes all numbers within the scope of this and any range within the scope of this, for example, 1 to 5 includes
1,1.1,1.3,1.5,2,2.75,3,3.80,4 and 5 etc..
Disclosure according to the present invention improves lithium metal-porous carbon composite mechanization preparation method, wherein
By selecting certain types of blender, the specific speed of agitator of selection and whipping temp etc., lithium carbon composite is improved
The consistency of yield and product.In addition, the present invention provides a kind of methods of system test lithium carbon composite.
According to the first aspect of the invention, a kind of method for producing lithium carbon composite in batches, the side are provided
Method includes successively carrying out the following steps under an inert atmosphere:
(1) lithium and porous carbon materials carrier are added sequentially in reaction kettle with 3: 1 to 1: 1 weight ratio；
(2) reaction kettle is heated to 200-220 DEG C of temperature, and will be reacted with the revolving speed of 1-3 revs/min of blender
Mixture in kettle stirs 1-3 minutes in advance；
(3) reaction kettle is heated to 230-280 DEG C of temperature, and will with the revolving speed of 300-700 revs/min of blender
Mixture in reaction kettle quickly stirs 20-60 minutes；With
(4) stop stirring and being cooled to room temperature reaction kettle, to obtain the lithium carbon composite.
In the present invention, a variety of blenders are used to carry out the above stirring to investigate the concrete type of blender to gained
The influence of the load lithium amount of product.As shown in fig. 1, used blender includes following various: dasher, turbine type are stirred
Mix device, anchor agitator, gate stirrer, screw blender and helix(ribbon type) agitator.The results show that being stirred when using anchor formula
Optimal product is achieved when device carries lithium amount.Therefore, certain specific embodiments according to the present invention, the blender are anchor formula
Blender.
Certain specific embodiments according to the present invention, used lithium is Battery grade lithium metal in the present invention.The electricity
Pond grade lithium metal is purchased from Tianjin China Energy Lithium Co., Ltd., purity 99.9%.
Certain specific embodiments according to the present invention, it is according to the present invention for producing the side of lithium carbon composite in batches
Porous carbon materials carrier employed in method is selected from one of the following or a variety of: carbon nanotube microballoon, carbon fiber microballoon,
Carbonaceous mesophase spherules, acetylene black carbosphere, Ketjen black carbosphere, porous active carbon microspheres etc..
Preferably, the porous carbon materials carrier is carbon nanotube microballoon.The carbon nanotube microballoon can be according to PCT state
Preparation method disclosed in border application publication number WO 2015139660A1 and Chinese Patent Application No. CN 201410395114.0
Preparation.The carbon nanotube microballoon has tiny spherical solid aggregated structure, spherical aggregated structure, spherical aggregated structure, more
Any one in hole spherical shape aggregated structure and bread figure aggregated structure.Preferably, the carbon nanotube microballoon is average straight
Diameter is 1 μm to 100 μm；And/or the conductivity of the carbon nanotube microballoon is 1 × 10-3To 103S·cm-1；And/or the carbon is received
The maximum allowable stress of mitron microballoon is 20MPa；And/or the specific surface area of the carbon nanotube microballoon is 100 to 1500m2/
g；And/or the aperture of hole contained by the carbon nanotube microballoon is 1nm to 200nm.
Certain specific embodiments according to the present invention, the carbon nanotube include multi-walled carbon nanotube, double wall carbon nano-tubes
Any one in pipe and single-walled carbon nanotube or two or more combinations.
It is according to the present invention for produce in batches lithium carbon composite method the step of (1) in, by lithium and porous carbon
Material support is added sequentially in reaction kettle.Wherein, the weight ratio of lithium and porous carbon materials carrier is 3: 1 to 1: 1, preferably 3: 1
To 2: 1, and more preferable 2.5: 1 to 2: 1.Pass through the model by the control of the weight ratio of lithium and porous carbon materials carrier 3: 1 to 1: 1
It encloses in the interior surface that can more effectively promote lithium metal to load to porous carbon materials carrier and hole.In addition, lithium metal and
The feeding sequence of porous carbon materials carrier is that lithium metal is first added, and adds porous carbon materials carrier, so that porous carbon materials carry
Body is covered on the surface of lithium metal, which does not turn-over.
The step of method according to the present invention for being used to produce in batches lithium carbon composite (2) is in pre- stirred autoclave
The step of material.The purpose of the step is so that lithium metal and porous carbon materials carrier tentatively mix.It is heated when by reaction kettle
To 200-220 DEG C, when preferably up to 200-210 DEG C of temperature, start the pre- stirring.In pre- stirring, with 70-100 revs/min
Clock, preferably 90-100 revs/min of revolving speed stir the mixture in reaction kettle 1-3 minutes, preferably 1-1.5 minutes in advance.
The step of method according to the present invention for being used to produce in batches lithium carbon composite (3) is in quick stirred autoclave
Material the step of.The purpose of the step is so that molten metal lithium and porous carbon materials carrier are sufficiently mixed uniformly.When
Reaction kettle is heated to 230-280 DEG C, when preferably 230-250 DEG C of temperature, starts the quick stirring.In quick stirring,
With 300-700 revs/min, preferably 400-500 revs/min of revolving speed quickly stirs the mixture in reaction kettle 20-60 minutes,
It is preferred that 20-40 minutes.
Above-mentioned technical proposal according to the present invention, it is anti-successively to carry out pre- stirring and two whipping steps progress of quick stirring
The purpose answered is: mixing slowly the surface for making carbon pipe microsphere powder be wrapped in molten metal lithium in advance, effectively avoids melting
The generation of lithium metal near-wall air curtain in high-speed agitating process.The yield of product can not only be improved, it is even more important that can be significant
Improve the load lithium amount and later period chemical property of carbosphere material.
Above-mentioned technical proposal according to the present invention, the blender are anchor agitator.
It is according to the present invention for produce in batches lithium carbon composite method the step of (4) in, stop stirring and
Reaction kettle is cooled to room temperature, to obtain the lithium carbon composite.To the step, lithium metal-porous carbon composite preparation
It finishes, the material in reaction kettle is lithium metal-porous carbon composite.The purpose of the step be to be off preparation process and
Cooling product.
The step of method according to the present invention for being used to produce in batches lithium carbon composite (1)-(4), needs in inert atmosphere
Middle progress.Certain specific embodiments according to the present invention, the inert atmosphere are argon gas, and wherein step (1)-(4) are in moisture
Content is not higher than 10ppm and oxygen content is not higher than in the glove box full of argon gas of 10ppm and carries out.
According to the second aspect of the invention, a kind of setting for method for above-mentioned batch production lithium carbon composite is provided
It is standby, comprising:
Reaction kettle；
Heating and attemperator, the heating and attemperator are for heating the reaction kettle and keeping its temperature；With
Agitating device, the agitating device are used to stir the material in the reaction kettle.
The function of reaction kettle is the place compound as molten metal lithium and porous carbon materials carrier.It is according to the present invention
Certain specific embodiments, the material of reaction kettle is stainless steel, and its heat resisting temperature is not less than 300 degrees Celsius.In addition, reaction
The wall thickness of kettle is about 1mm, and its bottom structure is flat or round bottom.The preferred embodiment of reaction kettle is by Weihai in Shandong province's Singapore dollar
The high-temperature high-pressure reaction kettle of work Machinery Co., Ltd. production.
The function of the heating and attemperator is the material in heating reaction kettle and reaction kettle, and can be in setting
The temperature of reaction kettle and material in reactor is maintained in time.
The function of agitating device is the material in preliminary stirred autoclave in pre- stirred autoclave in preparation step (1)
Material, the material in preparation step (3) quickly stirred autoclave, can sufficiently mix molten metal lithium and porous carbon support
It closes.The available mixing speed range of agitating device according to the present invention is 0-1000 revs/min.
In addition to this, the equipment optionally further includes controller, and the controller is for controlling the heating and heat preservation
The heating and heat preservation of device and the mixing speed and mixing time of the control agitating device.Integrated controller is not required
, if heating and attemperator can control temperature, agitating device can control mixing speed, then can omit integrated control
Device.
According to the third aspect of the invention we, a kind of system test method for lithium carbon composite, the side are provided
Method include to the lithium carbon composite about yield, carry lithium amount, pattern and pull out lithium plating lithium cycle performance test.Following
It will be described in measurement yield in content, carry lithium amount, pattern and the specific method and its result that pull out lithium plating lithium cycle performance.
The present invention is described in more detail below with reference to embodiment.It may be noted that these descriptions and embodiment are all
In order to be easy to understand the present invention, rather than limitation of the present invention.Protection scope of the present invention is with appended claims
It is quasi-.
Embodiment
In the present invention, mentioned " % " is " weight % ", and mentioned " part " is " parts by weight ".
Test method
In this disclosure, to the various lithium carbon composites obtained by batch manufacturing method about yield, load lithium
It amount, pattern and pulls out lithium plating lithium cycle performance etc. and is tested, specific test method is described as follows.
Yield
Gross mass in step (1) as the lithium of raw material is denoted as m1, by the porous carbon materials in step (1) as raw material
The quality of carrier is denoted as m2, and the lithium carbon composite quality obtained in step (4) as product is denoted as m3.
The calculation formula of yield are as follows:
Carry lithium amount
It weighs the lithium carbon composite prepared in m grams of step (4) and is compressed on the foam copper that diameter is 1.5cm
On, as cathode.The cathode is assembled into simulated battery with the metal lithium sheet as anode, wherein used electrolyte is
LiPF6It is dissolved in the mixed of the ethylene carbonate (EC) of volume ratio 1: 1: 1, dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC)
Solution obtained in bonding solvent.By the simulated battery with the electric current continuous discharge of 0.1mA, until voltage value is that 1V stopping is put
The capacity of electricity, process electric discharge is Q (current potential of capacity is coulomb).The load lithium in lithium carbon composite is calculated according to the following formula
Amount:
Pattern
By scanning electron microscope (SEM), (cold field emission of the model S4800 of Hitachi, Japan production scans electricity
Sub- microscope) observation lithium metal-porous carbon composite pattern, and pass through the grain of scanning electron micrograph statistics particle
Diameter distribution.
Pull out lithium plating lithium circulation
It weighs the lithium carbon composite prepared in m grams of step (4) and is compressed on the foam copper that diameter is 1.5cm
On, as cathode.The cathode is assembled into simulated battery with the metal lithium sheet as anode, wherein used electrolyte is
LiPF6It is dissolved in the mixed of the ethylene carbonate (EC) of volume ratio 1: 1: 1, dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC)
Solution obtained in bonding solvent.By obtained simulated battery in the cell tester (type of the new Weir Co., Ltd production in Shenzhen
Number cell tester for being CT-3008) on shelve 360 minutes, wherein with 1mA electric current constant-current charge (plating lithium) 1 hour, then with
1mA electric current constant-current discharge (pulling out lithium) 1 hour, cycle charging discharge process 200 times.
Embodiment 1
According to PCT International Publication No. WO 2015139660A1 and Chinese Patent Application No. CN 201410395114.0
Disclosed in preparation method prepare carbon nanotube microballoon.Obtained carbon nanotube microballoon has spherical aggregated structure, wherein institute
The average diameter for stating carbon nanotube microballoon is 5 μm, conductivity 10Scm-1, maximum allowable stress is 20MPa, specific surface area
For 255m2/ g, and the aperture of hole contained by the carbon nanotube microballoon is 20nm to 100nm.
Weigh carbon nanotube microballoon obtained in 10g Battery grade lithium metal and 5g above step.First lithium metal is put into instead
It answers in kettle (being produced by Singapore dollar chemical machinery Co., Ltd of Weihai in Shandong province), then carbon nanotube microballoon is put into reaction kettle.It is described
Reaction kettle is equipped with dasher (being produced by Singapore dollar chemical machinery Co., Ltd of Weihai in Shandong province).Start heating device, setting
Reaction temperature is 230 DEG C.It is 200 DEG C to temperature of reaction kettle, starts agitating device, the material in reaction kettle is stirred in advance,
Mixing speed is 100r/min (rev/min), and mixing time 1min, whipping process do not stop heating.It is to temperature of reaction kettle
230 DEG C, it is again started up mixing plant, mixing speed is 500r/min (rev/min), and mixing time is 20 minutes.Stop heating,
To reaction kettle cooled to room temperature, the product in reaction kettle is prepared lithium metal-porous carbon composite.Entire system
Standby process carries out in the glove box that argon gas is protected, and moisture content is lower than 10ppm, and oxygen content is lower than 10ppm.
According in the above Test Methods section about yield, carry lithium amount, pattern and pull out lithium plating lithium cycle performance etc. institute
The method of description tests obtained lithium metal-porous carbon composite.Fig. 2 shows the lithium carbon nanotube microballoon
The discharge curve of composite material.Fig. 3 shows the lithium-carbon nanotube microballoon composite material scanning electron microscope (SEM)
Photo, wherein the amplification factor of left figure is 1000 times, and the amplification factor of right figure is 18000 times.By calculating it is found that the lithium carbon
The yield of nanotube microballoon composite material is 66.7%, and carrying lithium amount is 39.3%.
Fig. 4 shows the lithium-carbon nanotube microballoon composite material prepared in embodiment 1 as the electricity of simulation manufactured by cathode
The constant current perseverance volume test curve in pond.From this figure, it can be seen that lithium-carbon nanotube microballoon composite material polarizing voltage when starting
Very little shows that material has big specific surface area, can greatly reduce current density, effectively inhibits the generation of lithium Zhi Jing.It avoids
Due to the brilliant short-circuit bring cell safety hidden danger of branch, to more likely be applied in actual high energy density cells system.
In addition, the result in embodiment 1 confirms the yield that can improve technique according to the technique and scheme of the present invention and carries lithium amount.
Embodiment 2
According to PCT International Publication No. WO 2015139660A1 and Chinese Patent Application No. CN 201410395114.0
Disclosed in preparation method prepare carbon nanotube microballoon.Obtained carbon nanotube microballoon has spherical aggregated structure, wherein institute
The average diameter for stating carbon nanotube microballoon is 5 μm, conductivity 10Scm-1, maximum allowable stress is 20MPa, specific surface area
For 255m2/ g, and the aperture of hole contained by the carbon nanotube microballoon is 20nm to 100nm.
Weigh carbon nanotube microballoon obtained in 10g Battery grade lithium metal and 5g above step.First lithium metal is put into instead
It answers in kettle (being produced by Singapore dollar chemical machinery Co., Ltd of Weihai in Shandong province), then carbon nanotube microballoon is put into reaction kettle.It is described
Reaction kettle is equipped with anchor agitator (being produced by Singapore dollar chemical machinery Co., Ltd of Weihai in Shandong province).Start heating device, setting
Reaction temperature is 230 DEG C.It is 200 DEG C to temperature of reaction kettle, starts agitating device, the material in reaction kettle is stirred in advance,
Mixing speed is 100r/min (rev/min), and mixing time 1min, whipping process do not stop heating.It is to temperature of reaction kettle
230 DEG C, it is again started up mixing plant, mixing speed is 500r/min (rev/min), and mixing time is 20 minutes.Stop heating,
To reaction kettle cooled to room temperature, the product in reaction kettle is prepared lithium metal-porous carbon composite.Entire system
Standby process carries out in the glove box that argon gas is protected, and moisture content is lower than 10ppm, and oxygen content is lower than 10ppm.
According in the above Test Methods section about yield, carry lithium amount, pattern and pull out lithium plating lithium cycle performance etc. institute
The method of description tests obtained lithium metal-porous carbon composite.Fig. 5 shows the lithium carbon nanotube microballoon
The discharge curve of composite material.Fig. 6 shows the lithium-carbon nanotube microballoon composite material scanning electron microscope (SEM)
Photo, wherein the amplification factor of left figure is 1000 times, and the amplification factor of right figure is 10000 times.By calculating it is found that the lithium carbon
The yield of nanotube microballoon composite material is 96.4%, and carrying lithium amount is 52.5%.
Fig. 7 shows the lithium-carbon nanotube microballoon composite material prepared in embodiment 2 as the electricity of simulation manufactured by cathode
The constant current perseverance volume test curve in pond.From this figure, it can be seen that lithium-carbon nanotube microballoon composite material polarizing voltage when starting
Very little shows that material has big specific surface area, can greatly reduce current density, effectively inhibits the generation of lithium Zhi Jing.It avoids
Due to the brilliant short-circuit bring cell safety hidden danger of branch, to more likely be applied in actual high energy density cells system.
In addition, the load lithium amount increase in embodiment 2 confirms that anchor agitator is suitable for according to the technique and scheme of the present invention the most.
Embodiment 3
According to PCT International Publication No. WO 2015139660A1 and Chinese Patent Application No. CN 201410395114.0
Disclosed in preparation method prepare carbon fiber microballoon.Obtained carbon fiber microballoon has spherical aggregated structure, wherein the carbon
The average diameter of fiber microballoon is 5 μm, conductivity 0.1Scm-1, maximum allowable stress is 20MPa, and specific surface area is
220m2/ g, and the aperture of hole contained by the carbon fiber microballoon is 20nm to 100nm.
Weigh carbon fiber microballoon obtained in 10g Battery grade lithium metal and 5g above step.Lithium metal is first put into reaction
In kettle (being produced by Singapore dollar chemical machinery Co., Ltd of Weihai in Shandong province), then carbon fiber microballoon is put into reaction kettle.The reaction
Kettle is equipped with anchor agitator (being produced by Singapore dollar chemical machinery Co., Ltd of Weihai in Shandong province).Start heating device, setting reaction
Temperature is 230 DEG C.It is 200 DEG C to temperature of reaction kettle, starts agitating device, the material in reaction kettle is stirred in advance, stirs
Speed is 100r/min (rev/min), and mixing time 1min, whipping process do not stop heating.It is 230 to temperature of reaction kettle
DEG C, it is again started up mixing plant, mixing speed is 500r/min (rev/min), and mixing time is 20 minutes.Stop heating, to
Reaction kettle cooled to room temperature, the product in reaction kettle are prepared lithium metal-porous carbon composite.Entire preparation
Process carries out in the glove box that argon gas is protected, and moisture content is lower than 10ppm, and oxygen content is lower than 10ppm.
According in the above Test Methods section about yield, carry lithium amount, pattern and pull out lithium plating lithium cycle performance etc. institute
The method of description tests obtained lithium metal-porous carbon composite.Fig. 8 shows that the lithium carbon fiber microballoon is multiple
The discharge curve of condensation material.Fig. 9 shows the lithium-carbon fiber microballoon composite material scanning electron microscope (SEM) photo,
Wherein the amplification factor of left figure is 1000 times, and the amplification factor of right figure is 10000 times.By calculating it is found that the lithium carbon fiber
The yield of microballoon composite material is 81.7%, and carrying lithium amount is 44.0%.
Figure 10 shows the lithium-carbon fiber microballoon composite material prepared in embodiment 3 as the electricity of simulation manufactured by cathode
The constant current perseverance volume test curve in pond.From this figure, it can be seen that lithium-carbon fiber microballoon composite material start when polarizing voltage very
It is small, show that material has big specific surface area, current density can be greatly reduced, effectively inhibits the generation of lithium Zhi Jing.Avoid by
In the brilliant short-circuit bring cell safety hidden danger of branch, to more likely be applied in actual high energy density cells system.It is real
The result confirmation for applying example 3 can be adapted for different types of porous carbon materials carrier according to the technique and scheme of the present invention.
Although specific embodiment has been shown and described in the present invention, those skilled in the art be will be understood that, can
To replace shown and described specific embodiment with various substitutions and/or equivalent embodiments, without departing from this hair
Bright range.The application is intended to include any improvement or change to the specific embodiment discussed in the present invention.Therefore, this hair
It is bright to be limited solely by claim and its equivalent.
It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, can carry out a variety of modifications and
Change.Such modifications and changes are intended to fall within the scope of the present invention as defined in the appended claims.
Claims (10)
1. a kind of method for producing lithium carbon composite in batches successively carries out following the method includes under an inert atmosphere
Step:
(1) lithium and porous carbon materials carrier are added sequentially in reaction kettle with 3: 1 to 1: 1 weight ratio；
(2) reaction kettle is heated to 200-220 DEG C of temperature, and will be reacted with the revolving speed of 70-100 revs/min of blender
Mixture in kettle stirs 1-3 minutes in advance；
(3) reaction kettle is heated to 230-280 DEG C of temperature, and will be reacted with the revolving speed of 300-700 revs/min of blender
Mixture in kettle quickly stirs 20-50 minutes.
2. the method according to claim 1 for producing lithium carbon composite in batches, wherein the blender is anchor formula
Blender.
3. the method according to claim 1 for producing lithium carbon composite in batches, wherein the porous carbon materials carry
Body is selected from one of the following or a variety of: carbon nanotube microballoon, carbon fiber microballoon, carbonaceous mesophase spherules, acetylene black carbon are micro-
Ball, Ketjen black carbosphere and porous active carbon microspheres.
4. the method according to claim 1 for producing lithium carbon composite in batches, wherein the porous carbon materials carry
Body is carbon nanotube microballoon.
5. the method according to claim 4 for producing lithium carbon composite in batches, wherein the carbon nanotube microballoon
With tiny spherical solid aggregated structure, spherical aggregated structure, spherical aggregated structure, porous spherical aggregated structure and bagel
Any one in shape aggregated structure.
6. the method according to claim 4 for producing lithium carbon composite in batches, in which:
The average diameter of the carbon nanotube microballoon is 1 μm to 100 μm；And/or
The conductivity of the carbon nanotube microballoon is 1 × 10-3To 103S·cm-1；And/or
The maximum allowable stress of the carbon nanotube microballoon is 20MPa；And/or
The specific surface area of the carbon nanotube microballoon is 100 to 1500m2/g；And/or
The aperture of hole contained by the carbon nanotube microballoon is 1nm to 200nm.
7. the method according to claim 4 for producing lithium carbon composite in batches, wherein the carbon nanotube includes
Any one in multi-walled carbon nanotube, double-walled carbon nano-tube and single-walled carbon nanotube or two or more combinations.
8. the method according to claim 1 for producing lithium carbon composite in batches, wherein the inert atmosphere is argon
Gas.
9. a kind of for setting to the method for producing lithium carbon composite described in any one of 8 in batches according to claim 1
It is standby, comprising:
Reaction kettle；
Heating and attemperator, the heating and attemperator are for heating the reaction kettle and keeping its temperature；With
Agitating device, the agitating device are used to stir the material in the reaction kettle.
10. equipment according to claim 9, wherein the equipment further includes controller, the controller is for controlling institute
State heating and the heating of attemperator and heat preservation, and the mixing speed and mixing time of the control agitating device.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710609084.2A CN109309197A (en) | 2017-07-26 | 2017-07-26 | Improve the method and its equipment of the yield of lithium carbon composite mass production |
| PCT/CN2017/105655 WO2019019408A1 (en) | 2017-07-26 | 2017-10-11 | Method for batch production of lithium-carbon composite material and device thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710609084.2A CN109309197A (en) | 2017-07-26 | 2017-07-26 | Improve the method and its equipment of the yield of lithium carbon composite mass production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109309197A true CN109309197A (en) | 2019-02-05 |
Family
ID=65201724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710609084.2A Pending CN109309197A (en) | 2017-07-26 | 2017-07-26 | Improve the method and its equipment of the yield of lithium carbon composite mass production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109309197A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05151969A (en) * | 1991-03-29 | 1993-06-18 | Honda Motor Co Ltd | Manufacture of negative electrode material for lithium battery |
| CN1830110A (en) * | 2003-07-29 | 2006-09-06 | Fmc公司 | Lithium metal dispersion in electrodes |
| CN105374991A (en) * | 2014-08-13 | 2016-03-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal lithium-framework carbon composite material and preparation method thereof, negative electrode and secondary battery |
| CN105789559A (en) * | 2016-04-21 | 2016-07-20 | 清华大学 | Flexible lithium metal cell negative pole and preparation method thereof |
| CN106063013A (en) * | 2014-03-06 | 2016-10-26 | 夏普株式会社 | Battery anode with preloaded metals |
| CN106663775A (en) * | 2014-02-13 | 2017-05-10 | 罗克伍德锂有限责任公司 | Galvanic cells and (partially) lithiated lithium battery anodes with increased capacity, and method for producing synthetic graphite intercalation connections |
| CN106711456A (en) * | 2015-11-12 | 2017-05-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Passivated lithium metal-carbon skeleton composite material and preparation method and application thereof |
-
2017
- 2017-07-26 CN CN201710609084.2A patent/CN109309197A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05151969A (en) * | 1991-03-29 | 1993-06-18 | Honda Motor Co Ltd | Manufacture of negative electrode material for lithium battery |
| CN1830110A (en) * | 2003-07-29 | 2006-09-06 | Fmc公司 | Lithium metal dispersion in electrodes |
| CN106663775A (en) * | 2014-02-13 | 2017-05-10 | 罗克伍德锂有限责任公司 | Galvanic cells and (partially) lithiated lithium battery anodes with increased capacity, and method for producing synthetic graphite intercalation connections |
| CN106063013A (en) * | 2014-03-06 | 2016-10-26 | 夏普株式会社 | Battery anode with preloaded metals |
| CN105374991A (en) * | 2014-08-13 | 2016-03-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal lithium-framework carbon composite material and preparation method thereof, negative electrode and secondary battery |
| CN106711456A (en) * | 2015-11-12 | 2017-05-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Passivated lithium metal-carbon skeleton composite material and preparation method and application thereof |
| CN105789559A (en) * | 2016-04-21 | 2016-07-20 | 清华大学 | Flexible lithium metal cell negative pole and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 赵临襄等: "《化学制药工艺学》", 31 August 2015 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103107315B (en) | A kind of nano-silicone wire/carbon composite material and preparation method thereof | |
| CN104810508B (en) | Cell negative electrode material and preparation method thereof | |
| CN104300125B (en) | The preparation method of one kind Punica granatum L. structural composite material | |
| CN104733708B (en) | A kind of preparation method of the nickle cobalt lithium manganate composite of Surface coating LiFePO4 | |
| CN106410177B (en) | A kind of elliposoidal SiOx/ graphite cathode composite materials and its preparation method and application | |
| CN109524648A (en) | A kind of porous carbon nanotube flexible battery material and preparation method thereof containing nano-silicon | |
| CN109309243A (en) | Lithium alloy-skeleton carbon composite material and preparation method, cathode and lithium battery | |
| CN105594026A (en) | Anode active material for lithium secondary battery, composition for anode including same, and lithium secondary battery | |
| CN102169987B (en) | Graphene-supported porous nickel oxide and preparation method thereof, and application of graphene-supported porous nickel oxide in lithium ion battery anode material | |
| CN113629245B (en) | Novel compounding method of carbon material and transition metal compound, composite material and application | |
| CN109616622A (en) | A kind of preparation method of carbon/tin/carbon tiny balloon lithium ion battery negative material | |
| CN109309201A (en) | Porous carbon skeleton-nano particle composite material, its lithium metal compound, their preparation method and application | |
| CN100383037C (en) | Carbon material and nano silicon composite materials and method for preparing same and use thereof | |
| CN107275578A (en) | A kind of method that use nitrogen-doped porous carbon material makes kalium ion battery negative pole | |
| Lu et al. | Yolk-shell Si/SiO x@ Void@ C composites as anode materials for lithium-ion batteries | |
| CN108554431A (en) | Co-N-C composite materials and its preparation based on Bio-MOF-11 and application | |
| CN108183213A (en) | A kind of preparation method of di-iron trioxide/carbon/carbon nanotube lithium battery negative material | |
| Shan et al. | Cu-CNTs current collector fabricated by deformation-driven metallurgy for anode-free Li metal batteries | |
| CN108428877A (en) | Nanometer Fe3O4@C In-situ reaction porous lithium ion cell negative materials and preparation method thereof | |
| CN102610809A (en) | Ferroferric oxide/graphite lithium ion battery anode material and preparation method for ferroferric oxide/graphite lithium ion battery anode material | |
| CN109585808A (en) | A kind of nanotube-shaped silica-base material and preparation and application with core-shell structure | |
| CN109411245A (en) | A kind of capacitor Cu2O/Mn3O4The preparation method of material | |
| CN106340630B (en) | A kind of SiO2The preparation method of/C composite nano materials and its application in lithium cell cathode material | |
| CN106159219B (en) | A kind of surface cladding LiTi2O4Lithium titanate material and preparation method thereof | |
| CN109309197A (en) | Improve the method and its equipment of the yield of lithium carbon composite mass production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190205 |
|
| RJ01 | Rejection of invention patent application after publication |