CN109950548A - A kind of carbon composite and its preparation method and application for secondary cell - Google Patents
A kind of carbon composite and its preparation method and application for secondary cell Download PDFInfo
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- CN109950548A CN109950548A CN201910248903.4A CN201910248903A CN109950548A CN 109950548 A CN109950548 A CN 109950548A CN 201910248903 A CN201910248903 A CN 201910248903A CN 109950548 A CN109950548 A CN 109950548A
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Abstract
The present invention provides a kind of carbon composite, preparation method and applications.The carbon composite that the carbon composite is made of soft carbon and hard carbon.When negative current collector using carbon composite provided by the invention as secondary cell, it can make the mutual supplement with each other's advantages of soft carbon and hard carbon, electroactive substance can be embedded in uniform sequentially in carbon composite, adsorbs or deposit, carbon material structural damage will not occur, will not there is a phenomenon where battery short circuits, while the performance of metal secondary batteries can be improved.The carbon composite not only can provide space for the deposition of metal, or insertion, absorption and the abjection of metal ion provide space or channel, improve the storage volume and cycle life of secondary cell.When carbon composite provided by the invention is used for the negative current collector of secondary cell, the original packaging technology of battery is had no need to change.
Description
Technical field
The invention belongs to field of batteries, and in particular to a kind of hard carbon for metal secondary batteries-soft carbon composite material and
Preparation method and application.
Background technique
With the development of the equipment such as portable electronic device and electric vehicle, need of the people to high-energy density energy storage device
It asks and increasingly increases.Therefore, the novel battery electrode material for developing the performances such as height ratio capacity, high magnification, high security is extremely urgent,
And carbon material becomes the preferred material of high energy density cells cathode due to having the characteristics that stable structure and cheap and easy to get.Mesh
Before, the carbon class material such as graphite, soft carbon, hard carbon is used for lithium ion battery by people, and some hard carbon materials are also in sodium ion
It is applied in battery.However, due to need to consider electrolyte to the compatibility issue of cell cathode and anode material, lithium from
When the carbon class material being used widely in sub- battery, sodium-ion battery is applied in the secondary cell for having metal deposit
Encounter many problems.For example, ethers electrolyte and lithium metal have good compatibility, but since ethers electrolyte cannot be in stone
The black effective solid electrolyte interface of Surface Creation (SEI) film, thus solvent molecule cannot be stopped to enter graphite by insertion altogether
Lattice leads to graphite dusting.Though simple hard carbon material will not be embedded in due to dusting altogether because of solvent, low, conductance that there are coulombic efficiencies
The problems such as rate is low and battery polarization.Therefore, it is necessary to develop and prepare the carbon material with composite construction, so that the two advantage is mutual
It mends, to improve the stability and battery performance of metal secondary batteries anode collector.
Summary of the invention
Therefore, the purpose of the present invention is to overcome the defects in the prior art, provides a kind of carbon composite, and its preparation
Methods and applications.
Before illustrating the content of present invention, it is as follows to define term used herein:
Term " soft carbon " refers to: the carbon material of graphite-structure can be converted by 2000 DEG C and the above high-temperature process.?
It also include artificial graphite and natural graphite in this patent.
Term " hard carbon " refers to: the carbon material of graphite-structure can not be converted into even across high-temperature process.
To achieve the above object, the first aspect of the present invention provides a kind of carbon composite, and the carbon composite is
The carbon composite being made of soft carbon and hard carbon, soft carbon and the ratio of hard carbon are 1:0.5~99.5 in the carbon composite, excellent
It is selected as 1:5~95.
Carbon composite according to a first aspect of the present invention, wherein the soft carbon material is selected from one or more of: people
Make graphite, natural graphite, petroleum coke, needle coke, pyrolytic carbon；
Preferably, the pyrolytic carbon is obtained by pyrolysis containing carbon matrix precursor；
It is highly preferred that described be selected from one or more of: coal tar, coal tar pitch, petroleum residual oil, petroleum containing carbon matrix precursor
Pitch, synthetic asphalts, anthracite, other organic compounds containing phenyl ring.
Carbon composite according to a first aspect of the present invention, wherein the hard carbon material is selected from one or more of: tree
Rouge carbon, carbon black, pyrolytic carbon；
Preferably, the pyrolytic carbon is obtained by pyrolysis containing carbon matrix precursor；
It is highly preferred that the carbonaceous presoma of the hard carbon material is selected from one or more of: synthetic resin, asphalt mixtures modified by epoxy resin
Rouge, aliphatic compound, sucrose, cellulose, lignin, glucose, starch, gelatin, other contain the organic compound of carbonyl.
Carbon composite according to a first aspect of the present invention, wherein the carbon composite has one or more of
Pattern: sheet, microballoon, porous structure, hollow microsphere, nanotube, hollow pipe, fiber；
The aperture of the carbon composite is all larger than 0.1nm, preferably 0.5nm~5000nm, and more preferably 1nm~
1000nm；
The specific surface area of the carbon composite is 10m2/ g~1000m2/ g, preferably 100m2/ g~500m2/g；With/
Or
The porosity of the carbon composite is 1%~99%, preferably 5%~90%.
Carbon composite according to a first aspect of the present invention, wherein further include in addition to carbon in the carbon composite
Other elements；
Preferably, the other elements be selected from one or more of: lithium, sodium, magnesium, silver, aluminium, potassium, calcium, iron, copper, titanium,
Tin, hydrogen, boron, nitrogen, oxygen, fluorine, silicon, phosphorus, sulphur.
The second aspect of the present invention provides the preparation method of carbon composite described in first aspect, which comprises
The soft carbon and the hard carbon material is compound in proportion；
Preferably, the complex method is selected from one or more of: mechanical mixture, core-shell structure, surface cladding, forerunner
Body mixing, presoma cladding；And/or
It is described compound to be realized by one or more of method: mechanical mixture, high temperature pyrolysis, vapor deposition.
The third aspect of the present invention provides a kind of collector, and the collector includes that carbon as described in relation to the first aspect is compound
Material.
The fourth aspect of the present invention provides the preparation method of collector described in the third aspect, and the method is selected from next
Kind is a variety of: self-supporting collector is made in the carbon composite；The carbon composite and binder are combined collection
Fluid；And/or the carbon composite is coated on current collector material surface, collector is made.
The fifth aspect of the present invention provides a kind of battery, the battery include carbon composite described in first aspect or
Collector described in the third aspect.
Battery according to a fifth aspect of the present invention, wherein the battery is secondary cell；Preferably, the battery is selected from
One or more of: serondary lithium battery, lithium-sulfur cell, lithium-air battery；Secondary sode cell, sodium-sulfur battery, sodium-air
Battery；Zinc-air battery, secondary potassium battery, secondary Mg battery, secondary aluminium cell, secondary zinc battery, zinc-manganese dioxide are secondary
Battery, magnesium-sulphur battery, aluminium-sulphur battery and solid/semi-solid lithium battery, solid/semi-solid serondary lithium battery, solid-state/half
Solid-state sode cell, solid/semi-solid secondary sode cell, the secondary potassium battery of solid/semi-solid, are consolidated solid/semi-solid potassium battery
State/semisolid zinc battery, solid/semi-solid secondary Mg battery, solid/semi-solid aluminum cell, is consolidated solid/semi-solid magnesium cell
State/semisolid secondary aluminium cell.
Battery according to a fifth aspect of the present invention, wherein the battery includes anode, bearing containing the carbon composite
Pole collector and the solid-state or semisolid being placed between positive and negative electrode or gel state or liquid electrolyte.
The problems of when for carbon material in metal secondary batteries for negative current collector, one object of the present invention
It is to provide a kind of improved carbon composite for secondary cell.When in the negative current collector of secondary cell contain this carbon
When composite material, electroactive substance can be embedded in uniform sequentially in carbon composite, adsorbs and deposit, and avoid afflux
Body structural damage improves specific capacity and collector to the compatibility of deposited metal, reduces deposition overpotential and battery polarization.?
In opposite process, due to the stable structure of carbon composite, these active materials can be deviate from and dissolve uniform sequentially, mention
The utilization rate of high active substance and the coulombic efficiency of battery.Meanwhile carbon composite itself can also be the deintercalation of metal ion
Space and channel are provided with deposition, improves the security performance, energy density and cycle life of metal secondary batteries.Of the invention is another
One purpose is to provide the preparation method and application of the carbon material.
The purpose of the present invention is what is be achieved through the following technical solutions.
On the one hand, the present invention provides a kind of carbon composite for secondary cell, which is by soft carbon and hard carbon
The carbon composite of composition, and the ratio between soft carbon and hard carbon is adjustable.
Carbon composite provided by the invention, ratio and structure between soft carbon and hard carbon can according to need any adjustment,
The structure and performance shortcomings of the carbon material of single structure are avoided, so that can have complementary advantages between soft carbon and hard carbon, is improved secondary
The comprehensive performance of battery.Meanwhile carbon composite itself can provide space and channel for the deintercalation of metal ion and deposition, mention
The energy density of high metal secondary cell.
The carbon composite provided according to the present invention, wherein the soft carbon material is selected from one or more of: natural stone
Ink, artificial graphite, petroleum coke, needle coke are also possible to the pyrolytic carbon obtained by pitch and organic compound containing phenyl ring.
The carbon composite provided according to the present invention, wherein the hard carbon material is selected from one or more of: resin
Carbon, carbon black, aliphatic compound pyrolytic carbon, saccharide compound pyrolytic carbon are also possible to the organic compound by containing carbonyl (- C=O)
The pyrolytic carbon that object and its derivative obtain.
The carbon composite provided according to the present invention, wherein the compositely proportional of soft carbon and hard carbon in the carbon composite
For 1:0.5~99.5, preferably 1:5~95.
The carbon composite provided according to the present invention, wherein soft carbon and hard carbon in the carbon composite can pass through
Pyrolysis is obtained containing carbon matrix precursor；
Preferably, the carbonaceous presoma of the soft carbon material is selected from one or more of: coal tar, coal tar pitch, petroleum
Residual oil, asphalt, synthetic asphalts, anthracite, the organic compound containing phenyl ring.
Preferably, the carbonaceous presoma of the hard carbon material be selected from one or more of: synthetic resin, epoxy resin,
Aliphatic compound, organic compound, sucrose, cellulose, lignin, glucose, starch, the gelatin for containing carbonyl (- C=O).
The carbon composite provided according to the present invention, wherein the carbon composite has certain shape characteristic；
Preferably, the pattern that the carbon composite has one or more of compound: sheet, microballoon, porous knot
Structure, hollow microsphere, nanotube, hollow pipe, fiber.
The carbon composite provided according to the present invention, wherein the carbon composite has the hole of certain size and quantity
Gap structure, aperture are all larger than 0.1nm, preferably 0.5nm~5000nm, more preferably 1nm~1000nm；And/or
The carbon composite has certain specific surface area, specific surface area 10m2/ g~1000m2/g, preferably
100m2/ g~700m2/g；Or its porosity is 1%~99%, preferably 5%~90%.
In some embodiments, the carbon composite is carbon fiber；In some embodiments, the carbon is multiple
Condensation material is carbon nanotube；In some embodiments, the carbon composite is porous carbon.
In some specific embodiments, the carbon composite is carbon fiber, the diameter of carbon fiber be 40nm~
900nm；In some specific embodiments, the carbon composite is carbon nanotube, the internal diameter of carbon nanotube is 10~
20nm, outer diameter are 30~50nm.
Carbon composite provided by the invention, wherein the example of the carbon composite include but is not limited to carbon fiber,
Carbon nanotube, porous carbon.
The carbon composite provided according to the present invention, wherein the carbon composite includes the carbon for keeping carbon material structure
Element and other elements ingredient, the atomicity percentage composition of other any single-elements is not higher than 20% in material, and the carbon is multiple
Other elements in condensation material include metallic element and/or nonmetalloid；
Preferably, the metallic element in the carbon composite include lithium, sodium, magnesium, silver, aluminium, potassium, calcium, iron, copper, titanium,
The combination of one or more of tin, barium.
Preferably, the nonmetalloid in the carbon composite includes hydrogen, boron, nitrogen, oxygen, fluorine, silicon, phosphorus, one in sulphur
Kind or several combinations.
In the present invention, the content of other elements can be according to the need of specifically used secondary cell in carbon composite
It wants and changes.For example, the element is compound in carbon for the carbon composite containing other elements for metal secondary batteries
Content (atomicity ratio) in material is generally no greater than 20%, preferably 1%~20%, more preferably 1%~10%.Accordingly
Ground, the content of carbon is 80% or more, preferably 99%~80%, preferably 99%~90% in carbon material.
In some embodiments, the carbon composite is the rich nitrogen carbon containing nitrogen；In some embodiments
In, the carbon composite is the oxygen-containing carbon containing oxygen element；In some embodiments, the carbon composite be containing
There is the carbon fiber of copper.
Carbon composite provided by the invention, wherein other elements in the example of the carbon composite include but
It is not limited to nitrogen, oxygen, copper.
On the other hand, the present invention also provides the complex methods of the carbon composite for secondary cell, described
It is in carbon composite that two kinds of carbon are compound in proportion, it will be described hard by the methods of mechanical mixture, core-shell structure, surface cladding
Carbon and soft carbon Material cladding can also be mixed by presoma, the modes such as presoma cladding are by the hard carbon presoma and soft
Carbon matrix precursor is compound and then is pyrolyzed.
The present invention also provides the preparation methods of the carbon composite for metal secondary batteries, by soft carbon or hard carbon
It mixes in proportion compound, obtains the carbon composite of corresponding proportion；And/or
Soft carbon (or hard carbon) is uniformly mixed into (solid-solid blend by a certain percentage with hard carbon presoma (or soft carbon presoma)
Or solid-liquid mixing), it then carries out high temperature pyrolysis and obtains the carbon composite of corresponding proportion；And/or
Soft carbon presoma is added in proportion in the hard carbon presoma (or soft carbon presoma) of the carbon material (or before hard carbon
Drive body) (solid-solid blend or solid-liquid mixing), a certain proportion of carbon composite is then obtained by high temperature pyrolysis；And/or
Carbonaceous gas decomposition is deposited in hard carbon or soft carbon surface and hole using vapour deposition process, obtains answering for cladded type
Carbon material is closed, i.e., with hard carbon packet soft carbon or with soft carbon packet hard carbon.And/or
The presoma (solid phase) that carbonaceous gas decomposition is deposited on hard carbon or soft carbon is coated using vapour deposition process, so
Pyrolysis obtains the complex carbon material of cladded type afterwards, i.e., with hard carbon packet soft carbon or with soft carbon packet hard carbon.And/or
By the soft carbon of the carbon material and hard carbon forerunner bluk recombination (solid-solid is compound, solid-liquid is compound or liquid-liquid is compound), so
Pyrolysis obtains the complex carbon material of cladded type afterwards.And/or
By pyrolyzed hard carbon or the vaporous precursors of soft carbon, soft carbon or hard carbon or the cladded type composite carbon of its presoma are obtained
Material.
In the preparation method of carbon composite provided by the invention, other elements during the preparation process, add before pyrolysis
Enter or is in itself present in presoma.
Another aspect, the present invention provides a kind of preparation method of collector containing the carbon composite, the sides
Method include the carbon composite is made with certain thickness self-supporting collector carry out using；And/or
By the carbon composite and some bonding agent class Material claddings, reach the laggard enforcement of certain thickness by roll-in
With；And/or
On some materials by carbon composite attachment, then roll-in uses after reaching certain thickness together；And/or
By the carbon composite coated in then carry out on current collector material (such as copper foil) surface using.
Another aspect, the present invention provides the carbon composites in metal secondary batteries such as serondary lithium battery, lithium-sulphur electricity
Pond, lithium-air battery；Secondary sode cell, sodium-sulfur battery, sodium-air battery；Zinc-air battery, secondary potassium battery, secondary magnesium
Battery, secondary aluminium cell, secondary zinc battery, zinc-manganese dioxide secondary cell, magnesium-sulphur battery, aluminium-sulphur battery and solid-state/
Semisolid lithium battery, solid/semi-solid sode cell, the secondary sode cell of solid/semi-solid, is consolidated solid/semi-solid serondary lithium battery
State/semisolid potassium battery, solid/semi-solid zinc battery, solid/semi-solid magnesium cell, is consolidated the secondary potassium battery of solid/semi-solid
Application in state/semisolid secondary Mg battery, solid/semi-solid aluminum cell, solid/semi-solid secondary aluminium cell etc..
In another aspect, the secondary cell is compound including anode, the carbon the present invention also provides a kind of secondary cell
Material is the metal negative electrode of collector and the solid-state or semisolid or gel state or liquid electrolyte that are placed between positive and negative electrode
And diaphragm.
The present invention does not have particular/special requirement to positive electrode, electrolyte and diaphragm material.In secondary cell provided by the invention
In, positive electrode conventional in the art, electrolyte and diaphragm material can be used.
Carbon composite provided by the invention can have but be not limited to it is following the utility model has the advantages that
1, the ratio of carbon composite provided by the invention, soft carbon and hard carbon can effectively regulate and control, carbon composite
Composite construction and ratio can be designed freely, for soft carbon in carbon composite and the regulation of the ratio of hard carbon provide it is effective compound and
Preparation method；
2, using the collector for containing carbon composite provided by the present invention for secondary cell as the secondary electricity of metal
When the negative current collector in pond, the metal ion in electrolyte can be embedded in, adsorb, deposit or deviate from carbon composite, is molten
Solution, will not recurring structure destruction, the phenomenon that not will cause battery short circuit, while the performance of metal secondary batteries can be improved；
3, carbon composite not only can provide space for metal deposit, or the insertion of metal ion, absorption and
Abjection provides space or channel, improves the storage volume of metal secondary batteries.The above-mentioned 3 points carbon for being conducive to design different proportion
Composite material, while the security performance and chemical property of metal secondary batteries can be improved；
4, when negative current collector provided by the present invention for the carbon composite of secondary cell as metal secondary batteries,
Have no need to change the original packaging technology of battery.
Detailed description of the invention
Hereinafter, carrying out the embodiment that the present invention will be described in detail in conjunction with attached drawing, in which:
Fig. 1 shows the photo of the carbon composite of embodiment 1.
Fig. 2 shows the photos of the scanning electron microscope of the carbon composite of embodiment 1.
Fig. 3 shows the Raman spectrum of the carbon composite of embodiment 1.
Fig. 4 shows Raman spectrum comparison diagram of the carbon composite of embodiment 1 before and after circulation.
Fig. 5 shows the photo of the scanning electron microscope of the carbon composite of embodiment 2.
Fig. 6 shows the Raman spectrum of the carbon composite of embodiment 2.
Fig. 7 shows the photo of the scanning electron microscope of the carbon composite of embodiment 3.
Fig. 8 shows the photo of the scanning electron microscope of the carbon composite of embodiment 5.
Fig. 9 shows the Raman spectrum of the carbon composite of embodiment 7.
Specific embodiment
Present invention will be further explained by specific examples below, it should be understood, however, that, these embodiments are only
It is used, is but should not be understood as present invention is limited in any form for specifically describing in more detail.
This part carries out general description to the material and test method that arrive used in present invention test.Although being
It realizes many materials used in the object of the invention and operating method is it is known in the art that still the present invention still uses up herein
It may detailed description.It will be apparent to those skilled in the art that within a context, if not specified, material therefor of the present invention and behaviour
It is well known in the art as method.
Reagent and instrument used in the following embodiment are as follows:
Polyacrylonitrile (PAN), dimethylformamide (DMF), Kynoar (PVDF), N-Methyl pyrrolidone (NMP),
Cobalt acid lithium, ethylene carbonate (EC), dimethyl carbonate (DMC), LiPF6, pitch, gelatin, vanadium phosphate sodium, NaClO4, carbonic acid diethyl
Ester (DEC), anthracite, resinous polymer, K3V2(PO4)2F3、KPF6, propene carbonate (PC), carbon nanotube sponge,
Li10GeP2S12, copper acetate, MgCoSiO4、Mg(AlCl2EtBu)2/ THF, sucrose, calcium carbonate, dilute hydrochloric acid, phenolic resin, MnO2,
ZnSO4, petroleum coke, graphene film, AlCl3, polyvinyl alcohol, polytetrafluoroethylene (PTFE) (PTFE), purchased from the limited public affairs of Beijing Yi Nuokai science and technology
Department；
Instrument:
Constant current charge-discharge test instrument is purchased from Wuhan Land Electronic Co., Ltd., model C T2001A.
Embodiment 1
The present embodiment is for illustrating carbon composite and its preparation method and application of the invention.
1. the carbon composite that preparation is used for lithium secondary battery
2g polyacrylonitrile (PAN) is dissolved in 20mL dimethylformamide (DMF), PAN is slowly added into DMF and stirs
It mixes 1 hour, fiber is made using electrostatic spinning technique in the solution after uniform dissolution, then by spinning product in Muffle furnace
280 DEG C pre-burning 2 hours, later again in tube furnace under argon gas (Ar) atmosphere 800 DEG C burn 6 hours.Obtained carbon composite
As shown in Figure 1.
As shown in Fig. 2, the pattern of obtained carbon composite is carbon fiber, specific surface area 82.89m2/ g, aperture
Range is 10~500nm, porosity 82%.It is tested using the carbon material that Raman spectrum obtains embodiment 1, as a result such as
Shown in Fig. 3, material is the composite construction of soft carbon and hard carbon.
2. lithium secondary battery preparation and electro-chemical test
Electrode slice preparation: by above-mentioned carbon composite grinding after, at normal temperatures and pressures with the N- of Kynoar (PVDF)
Methyl pyrrolidone (NMP) solution (concentration 50mg/mL) uniformly mixes (the weight ratio 9:1 of drying latter three), and slurry is made
Afterwards even application in copper foil current collector, obtain thickness 50 microns coating become electrode slice.By this electrode slice at 50 DEG C
It after drying, is compressed under 20Kg/cm2 pressure, is then washed into working electrode of the circle as simulated battery that diameter is 14mm.It will
Round pole piece after cutting becomes pole piece after drying 6h in 120 DEG C of vacuum drying ovens.Or
It is electric as the work of simulated battery that the carbon composite film of above-mentioned synthesis is directly washed into the circle that diameter is 14mm
Pole.Become pole piece after round pole piece after cutting to be dried to 6h in 120 DEG C of vacuum drying ovens.
The main member of battery includes positive plate, negative electrode tab and diaphragm three parts in the embodiment of the present invention.Porous septum is inserted
Enter between anode and cathode and filled with electrolyte.The battery case that one end of anode and cathode is burn-on respectively after lead with mutually insulated
Both ends or electrode column are connected.Button (single layer), cylindrical (multilaminate coiled), rectangular can be made in the battery of above-mentioned basic structure
Various shapes and specifications such as (stackings, Z-fold or multilaminate coiled).
Battery assembly: by such as working electrode of the basic building block in addition to electrolyte, abundant to electrode, diaphragm, battery case etc.
Simulated battery is assembled into after drying according to a conventional method.Using electrode slice manufactured in the present embodiment as negative current collector, made with cobalt acid lithium
For anode, with the perforated membrane (Celgard2300) of PP/PE or using glass fibre (Whatman) as diaphragm, electrolyte is mixing
Organic solvent ethylene carbonate (EC): dimethyl carbonate (DMC)=1:1 (v:v), electrolyte are the LiPF of 1mol/L6, it is being full of
Lithium secondary battery is assembled into the glove box of Ar gas.H in glove box2O content and O2Content is both less than 0.1ppm.
Constant current charge-discharge test is carried out to the battery of the present embodiment production, wherein test temperature is 25 DEG C, and current density is
20mA·g-1, charge and discharge are 3.0-4.2V by voltage.
Raman spectrum of the carbon composite after circulation 20 weeks and the comparison diagram before circulation that Fig. 4 is embodiment 1.Such as Fig. 4
Shown, after circulation 20 weeks, carbon material still maintains good composite construction.
1 loop test of embodiment after 100 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency protect
It holds 99.2% or so.
Embodiment 2
The present embodiment is for illustrating carbon composite and its preparation method and application of the invention.
1. the carbon composite that preparation is used for lithium secondary battery
1.8g PAN and 0.2g pitch is dissolved in 20mL DMF, PAN and pitch are slowly added into DMF and stir 1
Hour, nano wire is made using electrostatic spinning technique in the solution after uniform dissolution, then by spinning product 280 in Muffle furnace
DEG C pre-burning 2 hours, later again in tube furnace under argon atmosphere 800 DEG C burn 6 hours, used after being cooled to room temperature.
As shown in figure 5, the pattern of obtained carbon composite is carbon nanocoils, specific surface area 86.89m2/ g, hole
Diameter range is 5~500nm, porosity 83%.It is surveyed using the carbon material that Raman spectrum tester obtains embodiment 2
Examination, as a result as shown in fig. 6, material is the composite construction of soft carbon ratio increased soft carbon and hard carbon.
2. lithium secondary battery preparation and electro-chemical test
Electrode slice and assembled battery are made using with method identical in embodiment 1.With carbon nanometer manufactured in the present embodiment
Wire material is that deposition of the negative current collector for lithium metal uses concentration for the LiPF6 of 1mol/L using cobalt acid lithium as positive electrode
The solution for being dissolved in EC and DMC (volume ratio 1:1) is electrolyte, and assembling obtains lithium secondary battery.Constant current charge and discharge is carried out to the battery
Electrical testing, wherein test temperature is 25 DEG C, current density 20mAg-1, charge and discharge are 3.0-4.2V by voltage.
2 loop test of embodiment after 80 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency keep
99.3% or so.
Embodiment 3
The present embodiment is for illustrating carbon composite and its preparation method and application of the invention.
1. the carbon composite that preparation is used for sodium rechargeable battery
By gelatin and pitch 1:1 mechanical mixture in mass ratio, by obtained compounding substances in tube furnace under argon atmosphere
It is pyrolyzed 6 hours at 800 DEG C, the carbon composite containing nitrogen is obtained after natural cooling.
As shown in fig. 7, the pattern of obtained carbon composite is porous carbon, specific surface area 553.62m2/ g, hole
Diameter range is 1~100nm, porosity 67%.Raman test result shows that obtained carbon material is that soft carbon and hard carbon are compound
Material, obtained carbon material is rich nitrogen carbon material to photoelectron spectroscopy as the result is shown.
2. sodium rechargeable battery preparation and electro-chemical test
Electrode slice and assembled battery are made using with method identical in embodiment 1, it is more with rich nitrogen manufactured in the present embodiment
Hole carbon material is that deposition of the negative current collector for metallic sodium uses concentration for 1mol/L's using vanadium phosphate sodium as positive electrode
NaClO4The solution for being dissolved in EC and diethyl carbonate (DEC) (volume ratio 1:1) is electrolyte, and assembling obtains sodium rechargeable battery.It is right
The battery carries out constant current charge-discharge test, wherein test temperature is 25 DEG C, current density 20mAg-1, charge and discharge are by electricity
Pressure is 2.0-4.0V.
3 loop test of embodiment after 80 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency keep
99.0% or so.
Embodiment 4
The present embodiment is for illustrating carbon composite and its preparation method and application of the invention.
1. the carbon composite that preparation is used for potassium secondary cell
Anthracite powder is placed at lower 800 DEG C of argon atmosphere in tube furnace after Pintsch process, obtained sample is carried out
Mechanical lapping obtains soft carbon material.Curing agent is added into resinous polymer, grinds the sample after solidification to obtain powder.It will
After obtained powder is mixed with the soft carbon material that back obtains with mass ratio 5:100, by obtained mixed-powder in tube furnace
It is calcined 6 hours at lower 900 DEG C of middle argon atmosphere, natural cooling obtains the carbon composite that soft carbon is coated with hard carbon, pore diameter range
For 1~200nm, porosity 62%.
2. the preparation of potassium secondary cell and electro-chemical test
Electrode slice and assembled battery are made using with method identical in embodiment 1, with manufactured in the present embodiment with hard carbon
The carbon composite of packet soft carbon is the deposition that negative current collector is used for lithium metal, with K3V2(PO4)2F3For positive electrode, use is dense
Degree is the KPF of 1mol/L6The solution for being dissolved in EC and propene carbonate (PC) (volume ratio 1:1) is electrolyte, and assembling obtains potassium two
Primary cell.Constant current charge-discharge test is carried out to the battery, wherein test temperature is 25 DEG C, current density 20mAg-1, charge and discharge
Electricity is 2.0-4.2V by voltage.
4 loop test of embodiment after 90 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency keep
98.8% or so.
Embodiment 5
The present embodiment is for illustrating carbon composite and its preparation method and application of the invention.
1. the carbon composite that preparation is used for lithium secondary battery
2g PAN is dissolved in 20mL DMF, PAN is slowly added into DMF and stirs 1 hour, after uniform dissolution
Nano wire is made using electrostatic spinning technique in solution, then by spinning product in Muffle furnace 280 DEG C pre-burning 2 hours, Zhi Houzai
800 DEG C burning 6 hours under argon gas (Ar) atmosphere in tube furnace.
The carbon fiber of obtained self-supporting is washed into the disk that diameter is 14mm, with a thickness of 50 μm.Wherein, carbon nanocoils
Diameter is 200nm or so, specific surface area 113.56m2/ g, pore diameter range are 10~500nm, porosity 89%, such as Fig. 8
It is shown.Raman test result shows that obtained carbon material is soft carbon and the compound material of hard carbon.
2. lithium secondary battery preparation and electro-chemical test
Electrode slice and assembled battery are made using with method identical in embodiment 1.With carbon nanometer manufactured in the present embodiment
Wire material is that deposition of the negative current collector for lithium metal uses concentration for the LiPF of 1mol/L using cobalt acid lithium as positive electrode6
The solution for being dissolved in EC and DMC (volume ratio 1:1) is electrolyte, and assembling obtains lithium secondary battery.Constant current charge and discharge is carried out to the battery
Electrical testing, wherein test temperature is 25 DEG C, current density 20mAg-1, charge and discharge are 3.0-4.2V by voltage.
5 loop test of embodiment after 50 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency keep
99.2%.
Embodiment 6
The present embodiment is for illustrating carbon composite and its preparation method and application of the invention.
1. the carbon composite that preparation is used for sodium rechargeable battery
The carbon nanotube sponge of commercialization is washed into the disk that diameter is 14mm, with a thickness of 50 μm.Wherein, carbon nanotube
Internal diameter is 10~20nm, and outer diameter is 30~50nm.Show that carbon nanotube has three-dimensional structure by electron scanning micrograph,
Pore diameter range is 5~300nm, porosity 95%.By it is above-mentioned with carbon nanotube sponge make material use respectively dilute hydrochloric acid,
Deionized water and alcohol washes, then the carbon nano-tube material after cleaning, which is placed on room temperature in vacuum warehouse and is evacuated 12 hours, does it
It is dry.Raman test result shows that obtained carbon material is soft carbon and the compound material of hard carbon.
2. sodium rechargeable battery preparation and electro-chemical test
Electrode slice and assembled battery are made using with method identical in embodiment 1.With carbon nanometer manufactured in the present embodiment
Tube material is the deposition that negative current collector is used for metallic sodium, is anode with vanadium phosphate sodium, is dissolved in using the NaClO4 of 1molL-1
The mixed solution of EC and DEC (volume ratio 1:1) are electrolyte, and assembling obtains sodium rechargeable battery.Constant current charge and discharge is carried out to the battery
Electrical testing, wherein test temperature is 25 DEG C, current density 20mAg-1, and charge and discharge are 2.0-4.0V by voltage.
6 loop test of embodiment after 30 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency keep
96.7%.
Embodiment 7
The present embodiment is for illustrating carbon composite and its preparation method and application of the invention.
1. the carbon composite that preparation is used for all solid lithium secondary battery
1.5g PAN and 0.5g pitch is dissolved in 20mL DMF, PAN and pitch are slowly added into DMF and stir 1
Hour, fiber is made using electrostatic spinning technique in the solution after uniform dissolution, then by spinning product 280 DEG C in Muffle furnace
Pre-burning 2 hours, later again in tube furnace under argon gas (Ar) atmosphere 700 DEG C burn 6 hours.
The carbon fiber of obtained self-supporting is washed into the disk that diameter is 14mm, with a thickness of 80 μm.Wherein, carbon nanocoils
Diameter is 700nm or so, specific surface area 97.63m2/ g, pore diameter range are 5~500nm, porosity 87%.Raman
Test result shows that obtained carbon material is soft carbon and the compound material of hard carbon, as shown in Figure 9.
2. all solid lithium secondary battery preparation and electro-chemical test
Electrode slice and assembled battery are made using with method identical in embodiment 1.With carbon fiber manufactured in the present embodiment
Material is the deposition that negative current collector is used for lithium metal, is anode with cobalt acid lithium, using Li10GeP2S12For all solid state electrolyte,
Assembling obtains all-solid-state battery, tests the chemical property of the carbon fiber electrode.Wherein, test temperature is 25 DEG C, charge and discharge electricity
Current density is 10mAg-1, charging/discharging voltage range is 3.0-4.3V.
7 loop test of embodiment after 60 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency keep
97.6%.
Embodiment 8
The present embodiment is for illustrating carbon composite and its preparation method and application of the invention.
1. the carbon composite that preparation is used for Mg secondary cell
2g PAN is dissolved in 20mL DMF, PAN is slowly added into DMF and stirs 1 hour, while pressing 0.01mol/
Copper acetate is added in the concentration of L.Fiber is made using electrostatic spinning technique in solution after uniform dissolution, then spinning product exists
280 DEG C pre-burning 2 hours in Muffle furnace, later again in tube furnace under argon gas (Ar) atmosphere 800 DEG C burn 6 hours.
The carbon fiber of obtained self-supporting is washed into the disk that diameter is 14mm, with a thickness of 80 μm.Wherein, carbon nanocoils
Diameter is 900nm or so, specific surface area 102.75m2/ g, pore diameter range are 10~500nm, porosity 85%.It draws
Graceful test result shows that obtained carbon material is soft carbon and the compound material of hard carbon, and power spectrum is wherein joined by copper as the result is shown
It is miscellaneous.
2. Mg secondary cell preparation and electro-chemical test
Electrode slice and assembled battery are made using with method identical in embodiment 1.With carbon fiber manufactured in the present embodiment
Material is the deposition that negative current collector is used for magnesium metal, with MgCoSiO4For positive electrode, use concentration for 0.25molL-1's
Mg(AlCl2EtBu)2/ THF is electrolyte, and assembling obtains Mg secondary cell.Constant current charge-discharge test is carried out to the battery, wherein
Test temperature is 25 DEG C, current density 30mAg-1, charge and discharge are 0.5-2.1V by voltage.
8 loop test of embodiment after 70 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency keep
98.8%.
Embodiment 9
The present embodiment is for illustrating carbon composite and its preparation method and application of the invention.
1. the carbon composite that preparation is used for lithium secondary battery
By calcium carbonate and aqueous sucrose solution, (20ml, concentration are 1mol L-1) 1:1 mixed dissolution in mass ratio, 80 DEG C of stirrings
It is evaporated completely to aqueous solution.By the mixture after being evaporated in tube furnace under argon gas (Ar) atmosphere 800 DEG C burn 4 hours.With dilute salt
Remaining calcium carbonate and its decomposition product in thermal decomposition product are removed in pickling, and then drying grinding obtains the carbon composite wood containing oxygen element
Material, pore diameter range are 1~200nm, porosity 72%.
2. lithium secondary battery preparation and electro-chemical test
Electrode slice and assembled battery are made using with method identical in embodiment 1.With oxygen-containing carbon manufactured in the present embodiment
Composite material is that deposition of the negative current collector for lithium metal uses concentration for 1mol/L's using cobalt acid lithium as positive electrode
LiPF6The solution for being dissolved in EC and DMC (volume ratio 1:1) is electrolyte, and assembling obtains lithium secondary battery.Constant current is carried out to the battery
Charge-discharge test, wherein test temperature is 25 DEG C, current density 20mAg-1, charge and discharge are 3.0-4.2V by voltage.
9 loop test of embodiment after 100 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency protect
It holds 98.9% or so.
Embodiment 10
The present embodiment is for illustrating carbon composite and its preparation method and application of the invention.
1. the carbon composite that preparation is used for MH secondary battery
It is placed at lower 800 DEG C of argon atmosphere in tube furnace and is pyrolyzed 6 hours after phenolic resin is ground, ground after natural cooling
Carbon composite is obtained, pore diameter range is 1~100nm, porosity 63%.
2. MH secondary battery preparation and electro-chemical test
Electrode slice and assembled battery are made using with method identical in embodiment 1, it is compound with carbon manufactured in the present embodiment
Material is the deposition that negative current collector is used for metallic zinc, with MnO2For zinc secondary battery anode material, 1molL is used-1's
ZnSO4Aqueous solution be electrolyte, assembling obtain metal MH secondary battery, test the chemical property of the electrode.Wherein, it tests
Temperature is 25 DEG C, current density 30mAg-1, voltage range 0.8-2.0V.
10 loop test of embodiment after 60 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency protect
It holds 98.6% or so.
Embodiment 11
The present embodiment is for illustrating carbon composite and its preparation method and application of the invention.
1. preparation is used for aluminium-air secondary battery carbon composite
1.7g PAN and 0.3g petroleum coke is dissolved in 20mL DMF, PAN and petroleum coke are slowly added into DMF and stir
It mixes 1 hour, nano wire is made using electrostatic spinning technique in the solution after uniform dissolution, then by spinning product in Muffle furnace
280 DEG C pre-burning 2 hours, later again in tube furnace under argon gas (Ar) atmosphere 700 DEG C burn 6 hours.
The carbon nanocoils of obtained self-supporting are washed into the disk that diameter is 14mm, with a thickness of 80 μm.Wherein, carbon nanocoils
Diameter be 230nm or so, specific surface area 94.26m2/ g, pore diameter range are 5~500nm, porosity 82%.It draws
Graceful test result shows that obtained carbon material is soft carbon and the compound material of hard carbon.
2. aluminium-air secondary battery preparation and electro-chemical test
Electrode slice and assembled battery are made using with method identical in embodiment 1, it is compound with carbon manufactured in the present embodiment
Material is the deposition that negative current collector is used for metallic aluminium, take graphene film as the carrier of positive oxygen, with 0.1molL-1's
AlCl3 solution is that electrolyte assembles to obtain aluminium-air secondary battery.Wherein, test temperature is 25 DEG C, and control discharge capacity is
0.5mA·h。
11 loop test of embodiment after 40 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency protect
It holds 96.8%.
Embodiment 12
The present embodiment is for illustrating carbon composite and its preparation method and application of the invention.
1. the carbon composite that preparation is used for lithium secondary battery
2g polyvinyl alcohol is dissolved in 20mL dimethylformamide (DMF), polyvinyl alcohol is slowly added into DMF and stirs
It mixes 1 hour, fiber is made using electrostatic spinning technique in the solution after uniform dissolution, then by spinning product in Muffle furnace
280 DEG C pre-burning 2 hours, later again in tube furnace under argon gas (Ar) atmosphere 800 DEG C burn 6 hours.Raman spectrum institute as the result is shown
Material be hard carbon and soft carbon composite material, pore diameter range be 10~500nm, porosity 86%.
2. lithium secondary battery preparation and electro-chemical test
Electrode slice and assembled battery are made using with method identical in embodiment 1.With carbon fiber manufactured in the present embodiment
Material is that deposition of the negative current collector for lithium metal uses concentration for 1molL using cobalt acid lithium as positive electrode-1LiPF6
The solution for being dissolved in EC and DMC (volume ratio 1:1) is electrolyte, and assembling obtains lithium secondary battery.Constant current charge and discharge is carried out to the battery
Electrical testing, wherein test temperature is 25 DEG C, current density 20mAg-1, charge and discharge are 3.0-4.2V by voltage.
12 loop test of embodiment after 80 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency protect
It holds 99.1%.
Embodiment 13
The present embodiment is for illustrating carbon composite and its preparation method and application of the invention.
1. the carbon composite that preparation is used for lithium secondary battery
By calcium carbonate and aqueous sucrose solution, (20ml, concentration are 1mol L-1) 1:1 mixed dissolution in mass ratio, 80 DEG C of stirrings
It is evaporated completely to aqueous solution.By the mixture after being evaporated in tube furnace under argon gas (Ar) atmosphere 800 DEG C burn 4 hours.With dilute salt
Remaining calcium carbonate and its decomposition product in thermal decomposition product are removed in pickling, and then drying grinding obtains carbon composite, pore diameter range
For 10~500nm, porosity 74%.The carbon composite and polytetrafluoroethylene (PTFE) (PTFE) is compound in the ratio of 8:2,
By roll-in formed with a thickness of 100 μm of pole piece carry out using.
2. lithium secondary battery preparation and electro-chemical test
It is used for the deposition of lithium metal using carbon composite manufactured in the present embodiment as negative current collector, is anode with cobalt acid lithium
Material uses concentration for the LiPF of 1mol/L6The solution for being dissolved in EC and DMC (volume ratio 1:1) is electrolyte, and assembling obtains lithium two
Primary cell.Constant current charge-discharge test is carried out to the battery, wherein test temperature is 25 DEG C, current density 20mAg-1, charge and discharge
Electricity is 3.0-4.2V by voltage.
13 loop test of embodiment after 100 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency protect
It holds 98.8% or so.
Embodiment 14
The present embodiment is for illustrating carbon composite and its preparation method and application of the invention.
1. the carbon composite that preparation is used for lithium secondary battery
By calcium carbonate and aqueous sucrose solution, (20ml, concentration are 1mol L-1) 1:1 mixed dissolution in mass ratio, 80 DEG C of stirrings
It is evaporated completely to aqueous solution.By the mixture after being evaporated in tube furnace under argon gas (Ar) atmosphere 800 DEG C burn 4 hours.With dilute salt
Remaining calcium carbonate and its decomposition product in thermal decomposition product are removed in pickling, and then drying grinding obtains carbon composite, pore diameter range
For 10~500nm, porosity 76%.The carbon composite is compound by the method progress in embodiment 1 with PVDF, it will
Resulting compound coated on copper foil, then together by roll-in formed overlay with a thickness of 80 μm of pole piece carry out using.
2. lithium secondary battery preparation and electro-chemical test
It is used for the deposition of lithium metal using carbon composite manufactured in the present embodiment as negative current collector, is anode with cobalt acid lithium
Material uses concentration for the LiPF of 1mol/L6The solution for being dissolved in EC and DMC (volume ratio 1:1) is electrolyte, and assembling obtains lithium two
Primary cell.Constant current charge-discharge test is carried out to the battery, wherein test temperature is 25 DEG C, current density 20mAg-1, charge and discharge
Electricity is 3.0-4.2V by voltage.
14 loop test of embodiment after 100 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency protect
It holds 99.0% or so.
Although present invention has been a degree of descriptions, it will be apparent that, do not departing from the spirit and scope of the present invention
Under the conditions of, the appropriate variation of each condition can be carried out.It is appreciated that the present invention is not limited to the embodiments, and it is attributed to right
It is required that range comprising the equivalent replacement of each factor.
Claims (10)
1. a kind of carbon composite, which is characterized in that the carbon composite that the carbon composite is made of soft carbon and hard carbon,
Soft carbon and the ratio of hard carbon are 1:0.5~99.5, preferably 1:5~95 in the carbon composite.
2. carbon composite according to claim 1, which is characterized in that the soft carbon material is selected from following a kind of or more
Kind: artificial graphite, natural graphite, petroleum coke, needle coke, pyrolytic carbon；
Preferably, the pyrolytic carbon is obtained by pyrolysis containing carbon matrix precursor；
It is highly preferred that described be selected from one or more of: coal tar, coal tar pitch, petroleum residual oil, petroleum drip containing carbon matrix precursor
Blueness, synthetic asphalts, anthracite, other organic compounds containing phenyl ring.
3. carbon composite according to claim 1 or 2, which is characterized in that the hard carbon material be selected from it is following a kind of or
It is a variety of: resin carbon, carbon black, pyrolytic carbon；
Preferably, the pyrolytic carbon is obtained by pyrolysis containing carbon matrix precursor；
It is highly preferred that the carbonaceous presoma of the hard carbon material be selected from one or more of: synthetic resin, epoxy resin,
Aliphatic compound, sucrose, cellulose, lignin, glucose, starch, gelatin, other contain the organic compound of carbonyl.
4. carbon composite according to any one of claim 1 to 3, which is characterized in that the carbon composite has
One or more of pattern: sheet, microballoon, porous structure, hollow microsphere, nanotube, hollow pipe, fiber；
The aperture of the carbon composite is all larger than 0.1nm, preferably 0.5nm~5000nm, more preferably 1nm~1000nm；
The specific surface area of the carbon composite is 10m2/ g~1000m2/ g, preferably 100m2/ g~500m2/g；And/or
The porosity of the carbon composite is 1%~99%, preferably 5%~90%.
5. carbon composite according to any one of claim 1 to 4, which is characterized in that in the carbon composite also
Including the other elements in addition to carbon；
Preferably, the other elements be selected from one or more of: lithium, sodium, magnesium, silver, aluminium, potassium, calcium, iron, copper, titanium, tin,
Hydrogen, boron, nitrogen, oxygen, fluorine, silicon, phosphorus, sulphur.
6. the preparation method of carbon composite according to any one of claim 1 to 5, which is characterized in that the method
It include: that the soft carbon and the hard carbon material is compound in proportion；
Preferably, the complex method is selected from one or more of: mechanical mixture, core-shell structure, surface cladding, presoma are mixed
It closes, presoma cladding；And/or
It is described compound to be realized by one or more of method: mechanical mixture, high temperature pyrolysis, vapor deposition.
7. a kind of collector, which is characterized in that the collector includes that the carbon as described in any one of claims 1 to 5 is compound
Material.
8. the preparation method of collector according to claim 7, which is characterized in that the method is selected from following a kind of or more
Kind: self-supporting collector is made in the carbon composite；The carbon composite and binder are combined collector；
And/or the carbon composite is coated on current collector material surface, collector is made.
9. a kind of battery, which is characterized in that the battery include carbon composite described in any one of claims 1 to 5 and/
Or collector as claimed in claim 7.
10. battery according to claim 9, which is characterized in that the battery is metal secondary batteries；Preferably, described
Battery is selected from one or more of: serondary lithium battery, lithium-sulfur cell, lithium-air battery；Secondary sode cell, sodium-sulfur battery,
Sodium-air battery；Zinc-air battery, secondary potassium battery, secondary Mg battery, secondary aluminium cell, secondary zinc battery, zinc-titanium dioxide
Manganese secondary battery, magnesium-sulphur battery, aluminium-sulphur battery, solid/semi-solid lithium battery, solid/semi-solid serondary lithium battery, solid-state/
Semisolid sode cell, solid/semi-solid secondary sode cell, the secondary potassium battery of solid/semi-solid, are consolidated solid/semi-solid potassium battery
State/semisolid zinc battery, solid/semi-solid secondary Mg battery, solid/semi-solid aluminum cell, is consolidated solid/semi-solid magnesium cell
State/semisolid secondary aluminium cell.
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