CN109309243A - Lithium alloy-skeleton carbon composite material and preparation method, cathode and lithium battery - Google Patents
Lithium alloy-skeleton carbon composite material and preparation method, cathode and lithium battery Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The present invention provides a kind of lithium alloy-skeleton carbon composite material and preparation method, cathode and lithium battery.The lithium alloy-skeleton carbon composite includes on porous carbon materials carrier and the surface for being formed in the porous carbon materials carrier and intrapore lithium alloy.According to the technique and scheme of the present invention, compound by carrying out lithium alloy with skeleton carbon carrier, lithium metal can be effectively improved to the wellability of skeleton carbon, to improve the affinity of lithium metal and skeleton carbon, increase the load lithium amount in lithium material.
Description
Technical field
The present invention relates to energy battery field, specifically, the present invention provide a kind of lithium alloy-skeleton carbon composite and
Preparation method includes the lithium alloy-skeleton carbon composite cathode and lithium battery.
Background technique
Lithium ion battery has been widely used for the every field of today's society as the representative of clean energy resource.Lithium from
Sub- battery is due to characteristics such as high-energy density, environment friendly and good cyclical stabilities, by people's
Favor.However, with the development of society, the energy density of traditional lithium ion battery to can no longer meet people growing
Horsepower requirements.In addition, problem of environmental pollution is the maximum popular problem of today's society, the common recognition of present society is to develop clearly
The clean energy replaces traditional petroleum-based energy, therefore to develop the lithium dynamical battery with higher energy density be the current energy
The most important thing in field.
Since lithium anode has the specific capacity for decupling conventional graphite cathode, 3860mAh/g, and metal are reached
Lithium has most negative current potential and most light density, therefore will have great raising using the energy density of the battery of cathode of lithium.
In addition, lithium an- ode can provide lithium ion for anode, therefore can be with energy density higher no lithium anode such as sulphur, air
Deng lithium sulphur-lithium-air battery of composition high-energy density.If the battery is commercialized, energy density can and gasoline
It compares favourably, therefore environmental problem will be greatly improved.Unfortunately, lithium anode is easy to produce branch in cyclic process
Crystalline substance, with the progress that battery works, the dendrite constantly grown can pierce through battery diaphragm and cause battery short circuit and release huge
Heat causes a series of safety accidents such as burning, explosion.Furthermore the SEI layer on lithium metal surface in charge and discharge process is constantly grown
Active material and electrolyte are consumed, the cycle life of battery is reduced.
FMC Corp. of the U.S. prepares the gold that can be applied to lithium cell cathode material using the method for melting emulsification modified again
Belong to lithium particle (referring to US 8,021,496B2,102255080 A of 2013/0181160 US A1, CN).However utilize this method
The lithium metal grain diameter prepared is 20-100 microns, and partial size is larger and wider distribution, can not effectively inhibit lithium
The generation of dendrite.Meanwhile the material does not have the support of internal structure, and huge body can be generated in the charge and discharge process of large capacity
Product variation, is unfavorable for the cycle performance of battery.Suzhou Institute of Nano-tech. and Nano-bionics, Chinese Academy of Sciences discloses one kind
Lithium metal-skeleton carbon composite material and preparation method, cathode and secondary cell are (referring to PCT International Publication No. WO
2015139660A1；Chinese Patent Application No. CN 201410395114.0).Wherein, using stephanoporate framework carbon material as carrier
It is mixed with molten metal lithium, prepares lithium metal-skeleton carbon composite that particle size range is 1-100 microns, safety
It is substantially better than metal lithium sheet.However, the wellability of lithium metal and carbon skeleton is bad, the lithium metal prepared-skeleton carbon composite wood
The load lithium amount of material is low and specific capacity is low.Furthermore Yi Cui seminar is by CVD method on electrostatic spinning carbon fiber film surface
The close lithium of carbon material is improved by deposition Si or ZnO (referring to PNAS.1518188113, Nat.Commun.7:10992).
However this method needs the complicated processing of CVD, is difficult to produce in enormous quantities in the short time.
Therefore, a kind of load lithium amount that can be improved skeleton carbon composite, the method tool to improve specific capacity are developed
There is important meaning.
Summary of the invention
From technical problem described above, the purpose of the present invention is the lithium alloys by using melting to mix with skeleton carbon
It closes, lithium alloy-skeleton carbon compound cathode is prepared by simple and fast method, which improves the parent of lithium metal and skeleton carbon
And power, the load lithium amount of material is improved, and improve the specific capacity of material in turn.
The present inventor passes through thoroughgoing and painstaking research, completes the present invention.According to the technique and scheme of the present invention, by by one
The method that a little specific metallic elements and molten lithium are mixed with lithium alloy reduces the surface energy of lithium metal, so that lithium metal
More easily adhere in skeleton carbon, to obtain the higher lithium alloy of capacity-skeleton carbon composite.
According to an aspect of the invention, there is provided a kind of lithium alloy-skeleton carbon composite, the lithium alloy-skeleton
Carbon composite includes on porous carbon materials carrier and the surface for being formed in the porous carbon materials carrier and intrapore lithium
Alloy.
According to another aspect of the present invention, provide it is a kind of be used to prepare lithium alloy-skeleton carbon composite method,
The method includes successively carrying out the following steps under an inert atmosphere:
(1) by heating lithium metal to 180-220 DEG C of temperature, to obtain molten lithium；
(2) under the stirring of 500-800 revolutions per seconds of revolving speed, molten lithium obtained in step (1) is warming up to 220-1000
DEG C, one or more element meltings are added and obtain the lithium alloy of molten condition, the element of addition be selected from magnesium, silicon, boron, carbon,
Nitrogen, oxygen, fluorine, aluminium, phosphorus, sulphur, chlorine, calcium, zinc, gallium, germanium, arsenic, selenium, bromine, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, iridium,
One of platinum, gold, mercury, thallium, lead, bismuth and polonium are a variety of；
(3) molten is in in described obtained in the step (2) under the stirring of 500-800 revolutions per seconds of revolving speed
Porous carbon materials carrier is added in the lithium alloy of state, continues stirring 20-40 minutes, it is compound to obtain the lithium alloy-skeleton carbon
Material.
According to a further aspect of the invention, a kind of cathode for lithium battery is provided, wherein the material of the cathode
It is closed for the material of lithium alloy as described above-skeleton carbon composite or the cathode by being used to prepare lithium as described above
The preparation of gold-skeleton carbon composite method.
According to a further aspect of the invention, a kind of lithium battery is provided, the lithium battery pack contains to be used for as described above
The cathode of one-shot battery or secondary cell.
Compared with the prior art in this field, the present invention has the advantages that other specific by being added in molten lithium
Metallic element prepares lithium alloy, then lithium alloy and skeleton carbon progress is compound, is capable of forming and closes with the higher lithium for carrying lithium amount
Gold-skeleton carbon composite.The material can be kept substantially the original pattern of skeleton carbon (for example, spherical), partial size 5-30
Micron.In addition, surface of the lithium metal after forming alloy under its molten condition can reduce, thus more can easy and skeleton carbon materials
Expect it is compound, to improve the load lithium amount in skeleton carbon.
Detailed description of the invention
Fig. 1 shows the lithium magnesium alloy-skeleton carbon composite discharge curve prepared in embodiment 1 and according to WO
The comparison of lithium metal-skeleton carbon composite discharge curve of method preparation in 2015139660A1；
Fig. 2 shows that the lithium magnesium alloy-skeleton carbon composite scanning electron microscope (SEM) prepared in embodiment 1 is shone
Piece and EDS elemental analysis test result, in which: A is that the SEM of material morphology schemes；B is carbon distribution in composite material
EDS test chart；C is the EDS test chart of magnesium elements distribution in composite material, and the amplification factor in the above figure is 5000 times；
Fig. 3 shows the lithium magnesium alloy-skeleton carbon composite constant current charge-discharge test result prepared in embodiment 1 and root
According to the ratio of lithium metal-skeleton carbon composite constant current charge-discharge test result of the method preparation in WO 2015139660A1
Compared with；
Fig. 4 shows the Li-Si alloy-skeleton carbon composite discharge curve prepared in embodiment 2 and according to WO
The comparison of lithium metal-skeleton carbon composite discharge curve of method preparation in 2015139660A1；
Fig. 5 shows that the Li-Si alloy-skeleton carbon composite scanning electron microscope (SEM) prepared in embodiment 2 is shone
Piece and EDS elemental analysis test result, in which: A is that the SEM of material morphology schemes；B is carbon distribution in composite material
EDS test chart；C is the EDS test chart of element silicon distribution in composite material, and the amplification factor in the above figure is 5000 times；
With
Fig. 6 shows the Li-Si alloy-skeleton carbon composite constant current charge-discharge test result prepared in embodiment 2 and root
According to the ratio of lithium metal-skeleton carbon composite constant current charge-discharge test result of the method preparation in WO 2015139660A1
Compared with.
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..
According to the first aspect of the invention, a kind of lithium alloy-skeleton carbon composite, the lithium alloy-skeleton are provided
Carbon composite includes on porous carbon materials carrier and the surface for being formed in the porous carbon materials carrier and intrapore lithium
Alloy.
According to the technique and scheme of the present invention, the surface when lithium alloy is in molten state can be in melting lower than lithium metal
Surface energy when state.
According to the technique and scheme of the present invention, the lithium alloy that lithium metal is formed in the molten state with certain element-specifics has
Lower surface energy, thus when lithium alloy can be effectively increased to bone by the lithium alloy and framework carbon material carrier compound tense
The wellability of frame carbon improves affinity between the two, thus improve gained lithium alloy-skeleton carbon composite load lithium amount and
Specific capacity.
Certain technical solutions according to the present invention, the lithium alloy by by lithium metal and selected from magnesium, silicon, boron, carbon, nitrogen, oxygen,
Fluorine, aluminium, phosphorus, sulphur, chlorine, calcium, zinc, gallium, germanium, arsenic, selenium, bromine, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, iridium, platinum, gold,
One of mercury, thallium, lead, bismuth and polonium or multiple element are formed.Preferably, the element is magnesium or silicon.
Certain technical solutions according to the present invention, lithium alloy according to the present invention include the bianry alloy of lithium, such as lithium magnesium
Alloy, Li-Si alloy etc..When the lithium alloy is formed by lithium metal and another element, the weight percent of lithium in lithium alloy
Than being 70%~99.9%.It, can when the percentage of lithium metal and another metallic element controls in the above range
To effectively increase lithium alloy to the wellability of skeleton carbon.
Certain technical solutions according to the present invention, lithium alloy according to the present invention except above-described lithium bianry alloy with
It outside, further include ternary alloy three-partalloy such as the lithium magnalium, lithium gold and silver ternary alloy three-partalloy of lithium, the quaternary alloy of lithium such as lithium magnalium tin, lithium gold
Silver-colored platinum quaternary alloy, etc..When the lithium alloy is formed by lithium metal and other multiple element, in the lithium alloy, base
In the total weight of the lithium alloy, the weight percent of the other multiple element is 0.1-30 weight %, preferably 10-25 weight
Measure % and more preferably 10-15 weight %.When the weight percent of the other multiple element is controlled in range above
When, lithium alloy can be effectively increased to the wellability of skeleton carbon.
Certain technical solutions according to the present invention, lithium alloy according to the present invention are preferably lithium magnesium alloy or Li-Si alloy.
According to the present invention, lithium alloy has the wellability of enhancing to carbon skeleton in the molten state, carries lithium amount to increase.
Certain technical solutions according to the present invention, based on the lithium alloy-skeleton carbon composite total weight, the lithium alloy-bone
Lithium metal content in frame carbon composite is 45-95 weight %, preferably 57-62 weight % and more preferable 59-61 weight %.
According to the present invention, lithium alloy has the wellability of enhancing to carbon skeleton in the molten state, so that lithium closes unanimous-skeleton
The increase of carbon composite carries lithium amount, and then increases lithium alloy-skeleton carbon composite specific capacity.It is according to the present invention certain
Technical solution, the lithium alloy-skeleton carbon composite specific capacity are 1000-2470mAh/g.Wherein, for one-shot battery
For, lithium alloy-skeleton carbon composite specific capacity is preferably 1000-1200mAh/g, and for secondary cell,
Lithium alloy-skeleton carbon composite specific capacity is preferably 2210-2385mAh/g and more preferable 2272-2365mAh/g.
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, Super-P microballoon, porous active carbon microspheres, graphite microspheres, stone
Black alkene microballoon 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 bagel shape 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.
According to another aspect of the present invention, it provides and a kind of is used to prepare lithium alloy-skeleton carbon composite method, institute
Stating method includes successively carrying out the following steps under an inert atmosphere:
(1) by the melting temperature (180-220 DEG C) of heating lithium metal to lithium, to obtain molten lithium；
(2) under the stirring of 500-800 revolutions per seconds of revolving speed, molten lithium obtained in step (1) is warming up to 220-1000
DEG C, one or more element meltings are added and obtain the lithium alloy of molten condition, the element of addition be selected from magnesium, silicon, boron, carbon,
Nitrogen, oxygen, fluorine, aluminium, phosphorus, sulphur, chlorine, calcium, zinc, gallium, germanium, arsenic, selenium, bromine, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, iridium,
One of platinum, gold, mercury, thallium, lead, bismuth and polonium are a variety of；
(3) molten is in in described obtained in the step (2) under the stirring of 500-800 revolutions per seconds of revolving speed
Porous carbon materials carrier is added in the lithium alloy of state, continues stirring 20-40 minutes, it is compound to obtain the lithium alloy-skeleton carbon
Material.
According to the technique and scheme of the present invention, the lithium alloy that lithium metal is formed in the molten state with certain element-specifics has
Lower surface energy, thus when lithium alloy can be effectively increased to bone by the lithium alloy and framework carbon material carrier compound tense
The wellability of frame carbon improves affinity between the two, thus improve gained lithium alloy-skeleton carbon composite load lithium amount and
Specific capacity.
Certain technical solutions according to the present invention, the lithium alloy by lithium metal and selected from magnesium, silicon, boron, carbon, nitrogen, oxygen,
Fluorine, aluminium, phosphorus, sulphur, chlorine, calcium, zinc, gallium, germanium, arsenic, selenium, bromine, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, iridium, platinum, gold,
One of mercury, thallium, lead, bismuth and polonium or multiple element are formed.Preferably, the element or magnesium or silicon.
Certain technical solutions according to the present invention, lithium alloy according to the present invention include the bianry alloy of lithium, such as lithium magnesium
Alloy, Li-Si alloy etc..The weight percent of lithium is 70% to 99.9% in lithium alloy.When lithium metal and another described gold
When belonging to the percentage control of element in the above range, lithium alloy can be effectively increased to the wellability of skeleton carbon.
Certain technical solutions according to the present invention, lithium alloy according to the present invention except above-described lithium bianry alloy with
It outside, further include the ternary alloy three-partalloy such as lithium gold and silver ternary alloy three-partalloy of lithium, the quaternary alloy of lithium such as lithium Au-Ag-Pt quaternary alloy, etc.
Deng.When the lithium alloy is formed by lithium metal and other multiple element, in the lithium alloy, based on the total of the lithium alloy
Weight, the charged material weight percentage of the other multiple element are 0.1-30 weight %, preferably 10-25 weight % and more excellent
Select 10-15 weight %.It, can be effective when the charged material weight percentage of the other multiple element is controlled in range above
Increase lithium alloy to the wellability of skeleton carbon.
Certain technical solutions according to the present invention, lithium alloy according to the present invention are preferably lithium magnesium alloy or Li-Si alloy.
According to the present invention, lithium alloy has the wellability of enhancing to carbon skeleton in the molten state, carries lithium amount to increase.
Certain technical solutions according to the present invention, based on the lithium alloy-skeleton carbon composite total weight, the lithium alloy-bone
Lithium metal content in frame carbon composite is 45-95 weight %, preferably 57-62 weight % and more preferable 59-61 weight %.
According to the present invention, lithium alloy has the wellability of enhancing to carbon skeleton in the molten state, thus lithium alloy-skeleton
The increase of carbon composite carries lithium amount, and then increases lithium alloy-skeleton carbon composite specific capacity.It is according to the present invention certain
Technical solution, the lithium alloy-skeleton carbon composite specific capacity are 1000-2470mAh/g.Wherein, for one-shot battery
For, lithium alloy-skeleton carbon composite specific capacity is preferably 1000-1200mAh/g, and for secondary cell,
Lithium alloy-skeleton carbon composite specific capacity is preferably preferred 2210-2385mAh/g and more preferable 2272-2365mAh/
g。
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, Super-P microballoon, porous active carbon microspheres, graphite microspheres, stone
Black alkene microballoon 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 bagel shape 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.
According to a further aspect of the invention, a kind of cathode for lithium battery is provided, wherein the material of the cathode is
The material of lithium alloy-skeleton carbon composite as described above or the cathode by being used to prepare lithium alloy-as described above
It is prepared by the method for skeleton carbon composite.
According to a further aspect of the invention, a kind of lithium battery is provided, the lithium battery pack is used for one containing as described above
The cathode of primary cell or secondary cell.Preferably, the one-shot battery is lithium thermal cell, and the secondary cell is lithium metal-oxygen
Compound battery, lithium metal-polymer battery or rechargeable lithium ion batteries.
Following detailed description is intended to illustratively and in non-limiting manner illustrate the disclosure.
Specific embodiment 1 is a kind of lithium alloy-skeleton carbon composite, the lithium alloy-skeleton carbon composite packet
It includes porous carbon materials carrier and is formed on the surface of the porous carbon materials carrier and intrapore lithium alloy.
Specific embodiment 2 is the lithium alloy according to specific embodiment 1-skeleton carbon composite, wherein described
Lithium alloy by lithium metal and selected from magnesium, silicon, boron, carbon, nitrogen, oxygen, fluorine, aluminium, phosphorus, sulphur, chlorine, calcium, zinc, gallium, germanium, arsenic, selenium, bromine, ruthenium,
One of rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, iridium, platinum, gold, mercury, thallium, lead, bismuth and polonium or multiple element are formed.
Specific embodiment 3 is the lithium alloy according to specific embodiment 2-skeleton carbon composite, wherein working as institute
When stating lithium alloy and being formed by lithium metal and another element, the weight percent of lithium is 70%~99.9% in lithium alloy.
Specific embodiment 4 is the lithium alloy according to specific embodiment 2-skeleton carbon composite, wherein working as institute
When stating lithium alloy and being formed by lithium metal and other multiple element, in the lithium alloy, based on the total weight of the lithium alloy, institute
The weight percent for stating other multiple element is 0.1-30 weight %.
Specific embodiment 5 is the lithium alloy according to specific embodiment 2-skeleton carbon composite, wherein described
Lithium alloy is lithium magnesium alloy, Li-Si alloy, lithium-aluminium alloy, lithium boron alloy and other polynary derivatives.
Specific embodiment 6 is the lithium alloy according to specific embodiment 1-skeleton carbon composite, wherein being based on
The lithium alloy-skeleton carbon composite total weight, the lithium metal content in the lithium alloy-skeleton carbon composite are
45-95 weight %.
Specific embodiment 7 is the lithium alloy according to specific embodiment 1-skeleton carbon composite, wherein described
Lithium alloy-skeleton carbon composite specific capacity is 1000-2470mAh/g.
Specific embodiment 8 is the lithium alloy according to specific embodiment 1-skeleton carbon composite, wherein described
Porous carbon materials carrier is selected from one of the following or a variety of: carbon nanotube microballoon, carbon fiber microballoon, mesocarbon are micro-
Ball, acetylene black carbosphere, Ketjen black carbosphere, Super-P microballoon, porous active carbon microspheres, graphite microspheres and graphene microballoon.
Specific embodiment 9 is the lithium alloy according to specific embodiment 1-skeleton carbon composite, wherein described
Porous carbon materials carrier is carbon nanotube microballoon.
Specific embodiment 10 is the lithium alloy according to specific embodiment 9-skeleton carbon composite, wherein described
Carbon nanotube microballoon has tiny spherical solid aggregated structure, spherical aggregated structure, spherical aggregated structure, porous spherical aggregation
Any one in structure and bagel shape aggregated structure.
Specific embodiment 11 is the lithium alloy according to specific embodiment 9-skeleton carbon composite, 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.
Specific embodiment 12 is the lithium alloy according to specific embodiment 9-skeleton carbon composite, wherein described
Carbon nanotube includes any one or two or more groups in multi-walled carbon nanotube, double-walled carbon nano-tube and single-walled carbon nanotube
It closes.
Specific embodiment 13 be it is a kind of be used to prepare lithium alloy-skeleton carbon composite method, the method includes
The following steps are successively carried out under an inert atmosphere:
(1) by heating lithium metal to 180-220 DEG C of temperature, to obtain molten lithium；
(2) under the stirring of 500-800 revolutions per seconds of revolving speed, molten lithium obtained in step (1) is warming up to 220-1000
DEG C, one or more element meltings are added and obtain the lithium alloy of molten condition, the element of addition be selected from magnesium, silicon, boron, carbon,
Nitrogen, oxygen, fluorine, aluminium, phosphorus, sulphur, chlorine, calcium, zinc, gallium, germanium, arsenic, selenium, bromine, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, iridium,
One of platinum, gold, mercury, thallium, lead, bismuth and polonium are a variety of；
(3) molten is in in described obtained in the step (2) under the stirring of 500-800 revolutions per seconds of revolving speed
Porous carbon materials carrier is added in the lithium alloy of state, continues stirring 20-40 minutes, it is compound to obtain the lithium alloy-skeleton carbon
Material.
Specific embodiment 14 is that lithium alloy-skeleton carbon composite is used to prepare according to specific embodiment 13
Method, wherein when the lithium alloy is formed by lithium metal and another element, the weight percent of lithium in the lithium alloy
Than being 70% to 99.9%.
Specific embodiment 15 is that lithium alloy-skeleton carbon composite is used to prepare according to specific embodiment 13
Method, wherein when forming the lithium alloy by lithium metal and other multiple element, it is described based on the total weight of the lithium alloy
In addition the charged material weight percentage of multiple element is 0.1-30 weight %.
Specific embodiment 16 is that lithium alloy-skeleton carbon composite is used to prepare according to specific embodiment 13
Method, wherein the lithium alloy is lithium magnesium alloy, Li-Si alloy, lithium-aluminium alloy, lithium boron alloy and other polynary derivatives.
Specific embodiment 17 is that lithium alloy-skeleton carbon composite is used to prepare according to specific embodiment 13
Method, wherein based on the lithium alloy-skeleton carbon composite total weight, in the lithium alloy-skeleton carbon composite
Lithium metal content is 45-95 weight %.
Specific embodiment 18 is that lithium alloy-skeleton carbon composite is used to prepare according to specific embodiment 13
Method, wherein the lithium alloy-skeleton carbon composite specific capacity is 1000-2470mAh/g.
Specific embodiment 19 is that lithium alloy-skeleton carbon composite is used to prepare according to specific embodiment 13
Method, wherein the porous carbon materials carrier is selected from one of the following or a variety of: carbon nanotube microballoon, carbon fiber are micro-
Ball, carbonaceous mesophase spherules, acetylene black carbosphere, Ketjen black carbosphere, Super-P microballoon, porous active carbon microspheres, graphite microspheres
With graphene microballoon.
Specific embodiment 20 is that lithium alloy-skeleton carbon composite is used to prepare according to specific embodiment 13
Method, wherein the porous carbon materials carrier is carbon nanotube microballoon.
Specific embodiment 21 is that lithium alloy-skeleton carbon composite is used to prepare according to specific embodiment 20
Method, wherein the carbon nanotube microballoon has tiny spherical solid aggregated structure, spherical aggregated structure, spherical aggregation knot
Any one in structure, porous spherical aggregated structure and bagel shape aggregated structure.
Specific embodiment 22 is that lithium alloy-skeleton carbon composite is used to prepare according to specific embodiment 20
Method, 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.
Specific embodiment 23 is that lithium alloy-skeleton carbon composite is used to prepare according to specific embodiment 20
Method, 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 combination.
Specific embodiment 24 is a kind of cathode for lithium battery, wherein the material of the cathode is according to specific implementation
The material of lithium alloy described in any one of mode 1 to 12-skeleton carbon composite or the cathode is by according to specific implementation
The preparation of lithium alloy-skeleton carbon composite method is used to prepare described in any one of mode 13 to 23.
Specific embodiment 25 is a kind of lithium battery, and the lithium battery pack according to specific embodiment 24 containing being used for
The cathode of lithium battery.
Specific embodiment 26 is the lithium battery according to specific embodiment 25, and the lithium battery includes secondary electricity
Pond (such as lithium metal-oxide cell, lithium metal-polymer battery or rechargeable lithium ion batteries) and one-shot battery (such as lithium heat
Battery).
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 obtained various lithium alloys-skeleton carbon composite about load lithium amount, specific capacity, shape
Looks are tested with lithium plating lithium cycle performance etc. is pulled out, and specific test method is described as follows.
Carry lithium amount
It lithium alloy-skeleton carbon composite or lithium metal-skeleton carbon composite and is pressed prepared by weighing m grams
It makes on the foam copper that diameter is 1.5cm, as cathode.The cathode and the metal lithium sheet as anode are assembled into simulation electricity
Pond, wherein used electrolyte is LiPF6It is dissolved in ethylene carbonate (EC), the dimethyl carbonate of volume ratio 1: 1: 1
(DMC) and solution obtained in the mixed solvent of methyl ethyl carbonate (EMC).The simulated battery is continued with the electric current of 0.1mA
Electric discharge, until voltage value is that 1V stops electric discharge, the capacity of process electric discharge is Q (current potential of capacity is coulomb).According to following public affairs
Formula calculates the load lithium amount in lithium carbon composite:
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.In addition, carrying out EDS element point to lithium metal-porous carbon composite using the scanning electron microscope (SEM)
Analysis.
Pull out lithium plating lithium circulation
It lithium alloy-skeleton carbon composite or lithium metal-skeleton carbon composite and is pressed prepared by weighing m grams
It makes on the foam copper that diameter is 1.5cm, as cathode.The cathode and the metal lithium sheet as anode are assembled into simulation electricity
Pond, wherein used electrolyte is LiPF6It is dissolved in ethylene carbonate (EC), the dimethyl carbonate of volume ratio 1: 1: 1
(DMC) and solution obtained in the mixed solvent of methyl ethyl carbonate (EMC).Obtained simulated battery is (deep in cell tester
The cell tester of the model CT-3008 of Zhen Shi new Weir Co., Ltd production) 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.
Under an inert atmosphere, by 9g heating lithium metal to 220 DEG C so that it is melted.To in 800 revolutions per seconds of revolving speed
1g magnesium metal is added in the lithium of melting under stirring, continues stirring 20 minutes, the lithium of the content of magnesium of 10 weight % is obtained after cooling
Magnesium alloy.The lithium magnesium alloy of 10g is heated to its molten condition, and under the stirring in 800 revolutions per seconds of revolving speed
Carbon nanotube microballoon obtained in 5g above step is added in the lithium magnesium alloy of melting, continues stirring 40 minutes, it is cooling to product
After obtain lithium magnesium alloy-skeleton carbon composite.According to the above-described method for carrying lithium amount that calculates by calculating the lithium
Magnesium alloy-skeleton carbon composite load lithium amount is 64 weight %.
Respectively, according to the method in WO 2015139660A1, by 10g heating lithium metal to 180 DEG C so that its melt,
And carbon nanotube microballoon obtained in 5g above step is added into the lithium of melting, continues stirring 40 minutes, it is cooling to product
After obtain lithium-skeleton carbon composite.According to the above-described method for carrying lithium amount that calculates by calculating the lithium-skeleton carbon
The load lithium amount of composite material is that load lithium amount is 53 weight %.
Method described in lithium cycle performance etc. is plated with lithium is pulled out about pattern according in the above Test Methods section, it is right
Lithium magnesium alloy-skeleton carbon composite pattern derived above is tested with lithium plating lithium cycle performance is pulled out, and to above
Obtained lithium-skeleton carbon composite pulls out lithium plating lithium cycle performance and is tested.Fig. 1 shows the lithium magnesium prepared in embodiment 1
Alloy-skeleton carbon composite discharge curve and lithium metal-skeleton carbon according to the method preparation in WO 2015139660A1
The comparison of the discharge curve of composite material.Due to the lithium magnesium alloy that the lithium metal and magnesium metal of molten state are mixed to form reduce it is molten
Melt state metallic lithium surface energy, so that molten metal lithium is easier to enter the inside of framework carbon material, therefore lithium magnesium alloy-skeleton
Carbon compound cathode has higher specific capacity than lithium metal-framework carbon material.Fig. 2 shows the lithium magnesium alloy-prepared in embodiment 1
Scanning electron microscope (SEM) photo and EDS elemental analysis test result of skeleton carbon composite, in which: A is material shape
The SEM of looks schemes；B is the EDS test chart of carbon distribution in composite material；C is the EDS test chart of Mg distribution in composite material,
And the amplification factor in the above figure is 5000 times.By Fig. 2 (A) it is found that obtained lithium magnesium alloy-skeleton carbon/carbon composite material base
The spherical form of the porous carbon materials carrier as carrier is maintained in sheet.In addition, from the comparison of Fig. 2 (B) and (C) it is found that gold
The distribution and carbon for belonging to magnesium are distributed to coincide substantially, illustrates that magnesium metal is evenly distributed in the surface and hole of skeleton carbon.Fig. 3 is shown
Lithium magnesium alloy-skeleton carbon composite constant current charge-discharge test result for being prepared in embodiment 1 with according to WO
The comparison of lithium metal-skeleton carbon composite constant current charge-discharge test result of method preparation in 2015139660A1.From
The figure can be seen that lithium magnesium alloy-skeleton carbon composite polarizing voltage very little when starting, and show that material has big ratio table
Area can greatly reduce current density, effectively inhibit the generation of Li dendrite.And due to the presence of magnesium in alloy, in material
Inside plays the role of promoting lithium metal deposition, therefore the material is than the gold according to the method preparation in WO 2015139660A1
Belong to lithium-skeleton carbon composite and is provided with outstanding cyclical stability.
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.
Under an inert atmosphere, by 9g heating lithium metal to 220 DEG C so that it is melted.To in 500 revolutions per seconds of revolving speed
1g metallic silicon is added in the lithium of melting under stirring, is warming up to 600 DEG C, continues stirring 20 minutes, obtains 10 weight % after cooling
Silicone content Li-Si alloy.The Li-Si alloy of 10g is heated to its molten condition, and at 500 revolutions per seconds
Carbon nanotube microballoon obtained in 5g above step is added in the Li-Si alloy of melting under the stirring of revolving speed, continues 40 points of stirring
Clock obtains Li-Si alloy-skeleton carbon composite after product is cooling.Passed through according to the above-described method for carrying lithium amount that calculates
The Li-Si alloy-skeleton carbon composite load lithium amount known to calculating is 57 weight %.
Respectively, according to the method in W02015139660A1, by 10g heating lithium metal to 180 DEG C so that its melt, and
And carbon nanotube microballoon obtained in 5g above step is added into the lithium of melting, continue stirring 40 minutes, after product is cooling
Obtain lithium-skeleton carbon composite.It is multiple by calculating the lithium-skeleton carbon according to the above-described method for calculating load lithium amount
The load lithium amount of condensation material is that load lithium amount is 53 weight %.
Method described in lithium cycle performance etc. is plated with lithium is pulled out about pattern according in the above Test Methods section, it is right
Li-Si alloy derived above-skeleton carbon composite pattern is tested with lithium plating lithium cycle performance is pulled out, and to above
Obtained lithium-skeleton carbon composite pulls out lithium plating lithium cycle performance and is tested.Fig. 4 shows the lithium silicon prepared in embodiment 2
Alloy-skeleton carbon composite discharge curve and lithium metal-skeleton carbon according to the method preparation in WO 2015139660A1
The comparison of the discharge curve of composite material.Since the Li-Si alloy that the lithium metal and silicon of molten state are mixed to form reduces molten state
Metallic lithium surface energy, so that molten metal lithium is easier to enter the inside of framework carbon material, therefore Li-Si alloy-skeleton carbon is multiple
Closing cathode has higher specific capacity than lithium metal-framework carbon material.Fig. 5 shows the Li-Si alloy-skeleton prepared in embodiment 2
Scanning electron microscope (SEM) photo and EDS elemental analysis test result of carbon composite, in which: A is material morphology
SEM figure；B is the EDS test chart of carbon distribution in composite material；C is the EDS test chart of Si Elemental redistribution in composite material,
And the amplification factor in the above figure is 5000 times.By Fig. 5 (A) it is found that obtained Li-Si alloy-skeleton carbon/carbon composite material base
The spherical form of the porous carbon materials carrier as carrier is maintained in sheet.In addition, from the comparison of Fig. 5 (B) and (C) it is found that gold
The distribution and carbon for belonging to silicon are distributed to coincide substantially, illustrates that metallic silicon is evenly distributed in the surface and hole of skeleton carbon.Fig. 6 is shown
The Li-Si alloy prepared in embodiment 2-skeleton carbon composite constant current charge-discharge test result with according to WO
The comparison of lithium metal-skeleton carbon composite constant current charge-discharge test result of method preparation in 2015139660A1.From
The figure can be seen that Li-Si alloy-skeleton carbon composite polarizing voltage very little when starting, and show that material has big ratio table
Area can greatly reduce current density, effectively inhibit the generation of Li dendrite.And due to the presence of Silicon In Alloys, in material
Inside plays the role of promoting lithium metal deposition, therefore the material is than the gold according to the method preparation in WO 2015139660A1
Belong to lithium-skeleton carbon composite and is provided with outstanding cyclical stability.
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 lithium alloy-skeleton carbon composite, the lithium alloy-skeleton carbon composite include porous carbon materials carrier with
And it is formed on the surface of the porous carbon materials carrier and intrapore lithium alloy.
2. lithium alloy according to claim 1-skeleton carbon composite, wherein the lithium alloy is by lithium metal and is selected from
Magnesium, silicon, boron, carbon, nitrogen, oxygen, fluorine, aluminium, phosphorus, sulphur, chlorine, calcium, zinc, gallium, germanium, arsenic, selenium, bromine, ruthenium, rhodium, palladium, silver, cadmium, indium, tin,
One of antimony, tellurium, iodine, iridium, platinum, gold, mercury, thallium, lead, bismuth and polonium or multiple element are formed.
3. lithium alloy according to claim 2-skeleton carbon composite, wherein when the lithium alloy by lithium metal in addition
When a kind of formation of element, the weight percent of lithium is 70% to 99.9% in the lithium alloy.
4. lithium alloy according to claim 2-skeleton carbon composite, wherein when the lithium alloy by lithium metal in addition
When multiple element formation, in the lithium alloy, based on the total weight of the lithium alloy, the weight hundred of the other multiple element
Score is 0.1-30 weight %.
5. lithium alloy according to claim 2-skeleton carbon composite, wherein the lithium alloy is lithium magnesium alloy, lithium silicon
Alloy, lithium-aluminium alloy, lithium boron alloy and other polynary derivatives.
6. lithium alloy according to claim 1-skeleton carbon composite, wherein compound based on the lithium alloy-skeleton carbon
The total weight of material, the lithium metal content in the lithium alloy-skeleton carbon composite are 45-95 weight %.
7. lithium alloy according to claim 1-skeleton carbon composite, wherein the lithium alloy-skeleton carbon composite
Specific capacity be 1000-2470mAh/g.
8. a kind of be used to prepare lithium alloy-skeleton carbon composite method, the method includes under an inert atmosphere successively into
Row the following steps:
(1) by heating lithium metal to 180-220 DEG C of temperature, to obtain molten lithium；
(2) under the stirring of 500-800 revolutions per seconds of revolving speed, molten lithium obtained in step (1) is warming up to 220-1000 DEG C,
One or more element meltings are added and obtain the lithium alloy of molten condition, the element of addition be selected from magnesium, silicon, boron, carbon, nitrogen,
Oxygen, fluorine, aluminium, phosphorus, sulphur, chlorine, calcium, zinc, gallium, germanium, arsenic, selenium, bromine, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, iridium, platinum,
One of gold, mercury, thallium, lead, bismuth and polonium are a variety of；With
(3) in described in a molten state obtained in the step (2) under the stirring of 500-800 revolutions per seconds of revolving speed
Porous carbon materials carrier is added in lithium alloy, continues stirring 20-40 minutes, to obtain the lithium alloy-skeleton carbon composite.
9. a kind of cathode for lithium battery, wherein the material of the cathode is according to any one of claims 1 to 7
The material of lithium alloy-skeleton carbon composite or the cathode is used to prepare lithium alloy-by according to claim 8
It is prepared by the method for skeleton carbon composite.
10. a kind of lithium battery, the lithium battery pack is containing according to claim 9 for primary or serondary lithium battery negative
Pole.
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| CN110416526A (en) * | 2019-08-14 | 2019-11-05 | 戴嘉 | A kind of lithium cell cathode material and preparation method thereof |
| CN110797524A (en) * | 2019-11-08 | 2020-02-14 | 宁波致轻电池有限公司 | Multi-element lithium-magnesium alloy cathode material for secondary battery and adaptive electrolyte thereof |
| CN111180698A (en) * | 2019-12-31 | 2020-05-19 | 中国科学院宁波材料技术与工程研究所 | Metal lithium composite negative electrode, preparation method thereof and lithium metal secondary battery |
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Application publication date: 20190205 |