CN109411756A - A kind of secondary cell carbon three-dimensional structure electrode and its preparation method and application - Google Patents
A kind of secondary cell carbon three-dimensional structure electrode and its preparation method and application Download PDFInfo
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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Abstract
The present invention provides a kind of carbon three-dimensional structure electrode, preparation method and applications.When using the cathode provided by the invention for using carbon three-dimensional structure electrode as battery, active metal is deposited or is dissolved out on carbon material three-dimensional framework, will not generate corresponding metallic dendrite, is not in that dendrite pierces through the phenomenon that electrolyte causes battery short circuit；Hole abundant can accommodate the active metal being deposited on skeleton electrode and its volume expansion in three-diemsnional electrode, the rigid structure of three-dimensional framework itself makes electrode structure not lead to the collapsing of electrode structure because of the dissolution of active metal, and thus caused by battery volume change in shape, cycle life shortens and energy density reduces；Carbon material itself can provide space or channel for the insertion and abjection of metal ion, improve the storage volume of battery.When cathode provided by the present invention for carbon three-dimensional structure electrode as battery, 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 for the carbon three-dimensional structure electrode of secondary cell, its preparation side
Method and application.
Background technique
With the development of portable electronic device and electric vehicle, demand of the people to high-energy density energy storage device is increasingly
Increase.Secondary cell based on insertion chemistry is difficult to break through capacity bottleneck due to being embedded in the limitation of main crystal structure.Therefore,
People are turning to Research Emphasis all kinds of using metal as anode (cathode) activity based on reactive metal deposits and dissolution at present
The secondary cell of substance such as lithium-sulfur cell, sodium-sulfur battery, lithium-air (oxygen, similarly hereinafter) battery, sodium-air battery, zinc-sky
Pneumoelectric pond, potassium battery, magnesium cell, aluminum cell, zinc-manganese dioxide (MnO2) secondary cell, and (partly) solid metallic battery etc..
In these batteries, active metallic ion transmits in the electrolyte between positive and negative anodes, and deposits in metal negative electrode side
With dissolution.These metal negative electrode specific capacities usually with higher based on the electrochemical deposition of metal and dissolution, institute's structure
At secondary cell operating voltage with higher and energy density.However, due to deposition and process in leaching electrode current density
It is unevenly distributed, so that metal deposit or dissolution are uneven, to generate metallic dendrite during the deposition process, or in process in leaching
Middle dendrite fracture and peripheral activity metal or electrode lose electrical contact and form " isolated island ", reduce the security performance and use of battery
Service life.In a severer case, metallic dendrite can pierce through the diaphragm of battery or solid electrolyte causes battery short circuit, lead to electricity
Pond failure even combustion explosion.The growth for effectivelying prevent metallic dendrite is the key that guarantee all kinds of metal secondary batteries safeties institute
?.On the other hand, in the deposition and course of dissolution of active metal, the volume of electrode and battery is varied widely, and influences electricity
Electrical contact, active material utilization, battery cycle life and the battery applications in pond, it is therefore desirable to which the material with skeleton function is used
In the volume change for alleviating battery caused by dissolving metal deposition and electrode.
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 three-dimensional structure electrode, and its
Preparation method and application.
To achieve the above object, the first aspect of the present invention provides a kind of carbon three-dimensional structure electrode, and the electrode includes
Carbon material three-dimensional framework and the electroactive substance being attached on three-dimensional framework；
Preferably, the carbon material is selected from one or more of: carbon nanotube, carbon nanocoils, carbon fiber.
Electrode according to a first aspect of the present invention, wherein the carbon material three-dimensional framework with a thickness of 1 μm~1000 μm,
Preferably 5~100 μm, more preferably 10~50 μm；And/or
The porosity of the carbon material three-dimensional framework (when wherein without electroactive substance) is 50%~99%, preferably
It is 60%~95%.
Electrode according to a first aspect of the present invention, wherein the pipeline diameter of the carbon material is 20nm~10000nm, excellent
It is selected as 20nm~5000nm；
The length of the carbon material is 10~10000, preferably 100~2000；And/or
The ratio of amorphous carbon and graphitic carbon is (according to the representative in respective material Raman spectrum without fixed in the carbon material
The peak D of shape carbon and the integral area at the peak G for representing graphitic carbon calculate) it is 0.2~5.0, preferably 0.5~2.0.
Electrode according to a first aspect of the present invention, wherein the carbon material three-dimensional framework includes carbon material three-dimensional framework shape
At substrate and the coating that is formed by metal；
Preferably, the material one or more of of the coating: iron, gold, silver, copper, titanium, aluminium, nickel, iron, preferably iron,
Copper, nickel, titanium；
It is highly preferred that the coating with a thickness of 0~50nm, preferably 0~10nm.
Electrode according to a first aspect of the present invention, wherein the carbon three-dimensional structure electrode includes self-support type electrode and painting
Overlay on the electrode on other metal foils；
Preferably, the material of the metal foil is selected from one or more of: iron, gold, copper, aluminium, titanium, nickel, stainless steel,
Preferably iron, copper, aluminium, titanium, nickel, stainless steel.
Electrode according to a first aspect of the present invention, wherein the electroactive substance be electroactive metal and/or
Its alloy；
Preferably, the alloy is selected from the alloy that electroactive metal and electrochemically inactive material are constituted, in alloy
The total atom degree of active metallic element is not less than 20%；
It is highly preferred that the electroactive metal is selected from one or more of: lithium, sodium, potassium, magnesium, aluminium, zinc；
The electrochemically inactive material be selected from one or more of: boron, carbon, nitrogen, magnesium, aluminium, silicon, phosphorus, sulphur, titanium, manganese,
Iron, nickel, copper, zinc, silver, tin.
The second aspect of the present invention provides the preparation method of electrode described in first aspect, which comprises
Electroactive substance is filled in the carbon material three-dimensional framework；
Preferably, the fill method is selected from one or more of: electrochemical deposition, chemical plating, sputtering sedimentation, steaming
Plating.
The third aspect of the present invention provides a kind of battery, and the battery includes the electricity of carbon three-dimensional structure described in first aspect
Pole or the carbon three-dimensional structure electrode according to made from the preparation method of second aspect.
Battery according to a third 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, zinc-manganese dioxide secondary cell, Yi Jigu
State or the secondary potassium battery of the secondary sode cell of semisolid serondary lithium battery, solid/semi-solid, solid/semi-solid, solid/semi-solid
Secondary Mg battery, solid/semi-solid secondary aluminium cell.
Battery according to a third aspect of the present invention, wherein the battery includes that positive, described carbon three-dimensional structure electrode is negative
Pole and the solid-state or semisolid being placed between positive and negative electrode or gel state or liquid electrolyte.
For the above problem present in metal secondary batteries, it is an object of the present invention to provide a kind of improved use
In the electrode of metal secondary batteries.As metal secondary batteries electrode in use, electroactive metal uniform deposition is in carbon
In three-dimensional framework, the generation of metallic dendrite (such as Li dendrite) is avoided；During opposite, these active metals are uniformly dissolved out
Without fractureing or losing electrical contact with electrode matrix, the utilization rate of active metal and the coulombic efficiency of battery are improved.Together
When, carbon material itself can also provide space or channel for the insertion and abjection of metal ion, improve the safety of secondary cell
Energy, energy density and cycle life.It is a further object of the present invention to provide the preparation method and application of the electrode.
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 electrodes for secondary cell, and the electrode is by carbon material three-dimensional framework and divides
The electroactive substance composition being dispersed in three-dimensional framework.
Electroactive substance such as lithium metal effectively can be evenly distributed on carbon three-dimensional bone by electrode provided by the invention
The metallic dendrite (such as Li dendrite) generated in deposition and process in leaching in frame so as to avoid electroactive metal and raising
The utilization rate of active metal and the coulombic efficiency of battery, ensure that the safety of electrode structure integrality and battery.In addition, carbon materials
Material itself can also provide space or channel for the insertion and abjection of metal ion, improve the energy density of battery entirety.
The electrode provided according to the present invention, wherein the carbon material is carbon nanotube, in carbon nanocoils, carbon fiber
One kind or any combination thereof.
The electrode provided according to the present invention, wherein the carbon material three-dimensional framework with a thickness of 1 μm~1000 μm.
The electrode provided according to the present invention, wherein the porosity of the carbon material three-dimensional framework is 50%~99%.
The electrode provided according to the present invention, wherein the pipeline diameter of the carbon material is 10nm~10000nm, length/diameter
Than being 10~10000；
Preferably, the pipeline diameter of the carbon material is 20nm~5000nm, and length is 100~2000.
The electrode provided according to the present invention, wherein the ratio of amorphous carbon and graphitic carbon is (according to phase in the carbon material
Answer the representative amorphous carbon in material Raman spectrum the peak D and represent graphitic carbon the peak G integral area calculate) be 0.2~
5.0；
Preferably, the ratio of amorphous carbon and graphitic carbon is 0.5~2.0 in the carbon material.
The electrode provided according to the present invention, wherein the carbon material three-dimensional framework includes that carbon material three-dimensional framework is formed
Substrate and the coating that is formed by metal；
Preferably, the material of the coating is iron, gold, silver, copper, titanium, aluminium, nickel or iron, preferably copper, nickel and titanium；
Preferably, the coating with a thickness of 0~50nm, preferably 0~20nm.
The electrode provided according to the present invention, wherein the carbon three-dimensional structure electrode includes self-support type electrode and coating
Electrode on other metal foils；
Preferably, the metal foil be iron, gold, copper, aluminium, titanium, nickel or stainless steel, preferably iron, copper, aluminium, titanium,
Nickel, stainless steel.
In some embodiments, the carbon three-dimensional framework is carbon nanotube sponge；In some embodiments, described
Carbon three-dimensional framework be carbon nanotube paper；In some embodiments, the carbon three-dimensional framework is graphitized carbon fibre.
In some specific embodiments, the carbon three-dimensional framework is carbon nanotube sponge, and the internal diameter of carbon nanotube is
10~20nm, outer diameter are 30~50nm；In some specific embodiments, the carbon three-dimensional framework is carbon fiber, carbon fiber
Diameter be 500~800nm.
In some embodiments, the carbon three-dimensional framework is to be coated with iron, gold, silver, copper, titanium, aluminium, nickel or iron thin layer
Carbon nanotube, carbon nanocoils, carbon fiber etc.；In some specific embodiments, by iron, gold, silver, copper, titanium, aluminium, nickel or iron shape
At thickness of coating be 0~10nm.
The electrode provided according to the present invention, wherein the example of the carbon material includes but is not limited to that carbon nanotube, carbon are received
Rice noodles, carbon fiber.
The electrode provided according to the present invention, wherein the electroactive substance is by electroactive metal or its conjunction
Gold composition；
Preferably, the electroactive metal is lithium, sodium, potassium, magnesium, aluminium, zinc or any combination thereof；
Preferably, the alloy is selected from the metal of lithium, sodium, potassium, magnesium, aluminum and zinc or any combination thereof and electrochemically inactive
Or the alloy of nonmetallic composition, the total content (atomic ratio) of active metallic element is not less than 20% in alloy.
In the present invention, term " electroactive metal " refers to, for certain metal secondary batteries, and is being electrolysed
Certain metal cation travelled to and fro between positive and negative anodes in matter is corresponding, the gold that can be deposited and dissolve out in battery cathode
Belong to.When electrode provided by the invention is used for certain metal secondary batteries, in electrode only with travel to and fro between positive and negative anodes in the electrolytic solution
Between certain metal cation it is corresponding, the metal that can be deposited and dissolve out in battery cathode be electro-chemical activity gold
Belong to, and other metals or it is nonmetallic be not considered as " electro-chemical activity " or for " electrochemically inactive " or " nonactive ".
For example, only lithium metal is electroactive metal signified in the present invention in lithium metal secondary battery, and other metals or
Nonmetallic be not to be regarded as " electro-chemical activity " is (for example, in lithium metal secondary battery, although metallic aluminium can be with lithium shape
At alloy, with the electro-chemical activity on ordinary meaning, but in signified lithium metal battery of the invention, metallic aluminium is not in " electricity
The column of chemical activity " metal).
Electrode provided by the invention, wherein the example of the electroactive metal include but is not limited to lithium, sodium, potassium,
Magnesium, aluminum and zinc.
In some embodiments, the electrode contains one of lithium, sodium, potassium, magnesium, aluminum and zinc metal or several combinations
It forms；And in some embodiments, contain alloying component in the electrode.The alloy be selected from lithium, sodium, potassium, magnesium, aluminium and
Zinc or any combination thereof and the metal of electrochemically inactive or the alloy of nonmetallic composition.
In the present invention, the content of each electroactive metal can be according to the metal battery class being specifically applicable in alloy
Type and change.For example, for the metal secondary batteries using the preparation of a certain electroactive metal, which exists
Content (atomic ratio) in alloy is typically no less than 5%, preferably 10%~98%, more preferably 20%~90%.Correspondingly,
In alloy the content of other elements 90% hereinafter, preferably 2%~90%, preferably 10%~80%.
In some specific embodiments, the alloy by selected from lithium, sodium and potassium the first element and selected from boron, carbon, nitrogen,
Magnesium, aluminium, silicon, phosphorus, sulphur, titanium, manganese, iron, nickel, copper, zinc, silver, the second element of tin or second element group be combined into.The electrode
When for lithium battery, sode cell or potassium battery, the content (atomic ratio) of corresponding first element is not less than 5%, preferably 10%
~98%, more preferably 20%~90%；And the content of second element 90% hereinafter, preferably 2%~90%, more preferably
10%~80%.And electrode of the invention is for magnesium cell, aluminum cell or when zinc battery, the content of corresponding second element is not small
In 5%, preferably 10%~98%, more preferably 20%~90%；And the content of the first element is not higher than 90%, preferably
2%~90%, more preferably 10%~80%.
On the other hand, the present invention also provides the secondary cell preparation methods of carbon three-dimensional structure electrode, in three-dimensional
Electroactive substance is filled in skeleton, it is by electrochemical deposition, chemical plating, vapor deposition or sputtering method etc. that the electrochemistry is living
Property substance is filled into the carbon material three-dimensional framework.
Another aspect, the present invention provides the electrodes in metal secondary batteries such as serondary lithium battery, lithium-sulfur cell, lithium-
Air cell；Secondary sode cell, sodium-sulfur battery, sodium-air battery；Zinc-air battery, secondary potassium battery, secondary Mg battery,
Secondary aluminium cell, zinc-manganese dioxide secondary cell and the secondary sodium electricity of solid/semi-solid serondary lithium battery, solid/semi-solid
Answering in pond, the secondary potassium battery of solid/semi-solid, solid/semi-solid secondary Mg battery, solid/semi-solid secondary aluminium cell etc.
With.
In another aspect, the metal secondary batteries include anode, this hair the present invention also provides a kind of metal secondary batteries
Bright electrode is as cathode and the solid-state or semisolid or gel state or liquid electrolyte that are placed between positive and negative electrode.
The present invention does not have particular/special requirement to positive electrode, electrolyte and diaphragm material.It is secondary in metal provided by the invention
In battery, positive electrode conventional in the art, electrolyte and diaphragm material can be used.
Carbon three-dimensional structure electrode of the present invention can have but be not limited to it is following the utility model has the advantages that
1, the cathode using the carbon three-dimensional structure electrode provided by the present invention for secondary cell as metal secondary batteries
When, active metal is deposited or is dissolved out on carbon material three-dimensional framework, will not generate corresponding metallic dendrite, is not in dendrite thorn
Wear the phenomenon that electrolyte causes battery short circuit；
2, hole abundant can accommodate the active metal being deposited on skeleton electrode and its volume expansion in three-diemsnional electrode,
The rigid structure of three-dimensional framework itself makes electrode structure not lead to the collapsing of electrode structure because of the dissolution of active metal, and by
This caused battery volume change in shape, cycle life shorten and energy density reduces；
3, carbon material itself can provide space or channel for the insertion and abjection of metal ion, improve metal secondary batteries
Storage volume.The above-mentioned 3 points security performances and chemical property for being conducive to improve metal secondary batteries.
4, when cathode provided by the present invention for the carbon three-dimensional structure electrode of secondary cell as metal secondary batteries, 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 electrode of embodiment 1.
Fig. 2 shows the photos of the scanning electron microscope of the electrode of embodiment 1.
Fig. 3 shows the photo of the scanning electron microscope of the lithium deposition after the first week charging of electrode of embodiment 1.
Fig. 4 shows the electron scanning micrograph of the lithium deposition after electrode cycle 30 weeks of embodiment 1.
Fig. 5 show electrode cycle 30 weeks of embodiment 1 after, lithium dissolution after substrate scanning electron microscope shine
Piece.
Fig. 6 shows the photo of the scanning electron microscope of the electrode of embodiment 3.
Fig. 7 shows the photo of the scanning electron microscope of the electrode 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: reagent:
Carbon nanotube sponge, graphitized carbon fibre, carbon nanocoils piece, carbon cloth, carbon nanotube paper, carbon nanocoils paper,
Purchased from Nanjing Xian Feng Nono-material Science & Technology Ltd.；
LiCoO2, LiPF6, ethylene carbonate, dimethyl carbonate, vanadium phosphate sodium, NaPF6, cobalt acid lithium, Li10GeP2S12,
MgCoSiO4, Mg (AlCl2EtBu)2, THF, K3V2(PO4)2F3, KPF6, propene carbonate, MnO2, ZnSO4, graphene film, KOH,
Pure copper foil is purchased from Beijing Yi Nuokai Science and Technology Ltd.；
Hydrochloric acid, alcohol, citric acid are purchased from Sinopharm Chemical Reagent Co., Ltd..
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 electrode of the present invention and its preparation method and application.
1. the carbon nanotube three-dimensional structure electrode that production is used for lithium secondary battery
The carbon nanotube sponge of commercialization is washed into the disk that diameter is 14mm, with a thickness of 2 μm.Wherein, carbon nanotube
Internal diameter is 20nm, outer diameter 40nm, and the ratio of amorphous carbon and graphitic carbon is 0.74 in material.Diameter is the carbon nanotube of 14mm
Sponge electrode is as shown in Figure 1.
As shown in Fig. 2, obtained carbon nanotube sponge electrode has three-dimensional structure, porosity 95%.It will be above-mentioned
Carbon nanotube sponge electrode uses dilute hydrochloric acid, deionized water and alcohol washes respectively, then by the carbon nanotube sponge electricity after cleaning
Pole is placed on room temperature pumping 12h in vacuum warehouse and makes it dry.
2. lithium metal secondary battery
Using carbon nanotube sponge electrode manufactured in the present embodiment as cathode, with LiCoO2For positive electrode, use concentration for
1mol·L-1LiPF6The solution for being dissolved in ethylene carbonate (EC) and dimethyl carbonate (DMC) (volume ratio 1:1) is electrolyte,
Assembling obtains lithium metal secondary battery.
3. lithium metal secondary battery electro-chemical test
Constant current charge-discharge test is carried out to full battery, wherein test temperature is 25 DEG C, current density 20mAg-1, fill
Electric discharge is 3.0-4.2V by voltage.
Fig. 3 is that the scanning electron microscope of lithium deposition of the carbon nanotube sponge electrode of embodiment 1 after first week charging is shone
Piece.As shown in figure 3, lithium metal is deposited in the three-dimensional framework of carbon nanotube sponge electrode, and there is no lithium metal branch outside skeleton
Crystalline substance is formed.
Fig. 4 is that the scanning electron microscope of lithium deposition of the carbon nanotube sponge electrode of embodiment 1 after circulation 30 weeks is shone
Piece.It is deposited in three-dimensional framework as shown in figure 4, lithium metal is still controllable after circulation 30 weeks, and without gold outside skeleton
Belong to Li dendrite.
Fig. 5 is that the scanning electron microscope of lithium dissolution of the carbon nanotube sponge electrode of embodiment 1 after circulation 30 weeks is shone
Piece.As shown in figure 5, very clean inside carbon nano tube surface and three-dimensional framework after lithium dissolution, substantially without lithium metal remnants, this
Illustrate the basic completely reversibility dissolution of lithium metal.
1 loop test of embodiment after 80 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency keep
98.2%.
Embodiment 2
The present embodiment is for illustrating electrode of the present invention and its preparation method and application.
1. the graphitized carbon fibre three-dimensional structure electrode that production is used for lithium secondary battery
The graphitized carbon fibre of commercialization is washed into the disk that diameter is 14mm, with a thickness of 3 μm.Wherein, carbon fiber is straight
Diameter is 500nm, and the ratio of amorphous carbon and graphitic carbon is 0.51 in material.
The graphitized carbon fibre electrode that embodiment 2 is observed by scanning electron microscope, is graphitized carbon fiber as the result is shown
Dimension has three-dimensional structure, porosity 90%.
Above-mentioned graphitized carbon fibre electrode is used into citric acid, deionized water and alcohol washes respectively, it then will be after cleaning
Graphitized carbon fibre electrode is placed on room temperature pumping 12h in vacuum warehouse and makes it dry.
2. lithium metal secondary battery
Using graphitized carbon fibre electrode manufactured in the present embodiment as cathode, with LiCoO2For positive electrode, use concentration for
The LiPF of 1molL-16The solution for being dissolved in ethylene carbonate (EC) and dimethyl carbonate (DMC) (volume ratio 1:1) is electrolyte,
Assembling obtains lithium metal secondary battery.
3. lithium metal secondary battery electro-chemical test
Constant current charge-discharge test is carried out to full battery, wherein test temperature is 25 DEG C, current density 20mAg-1, fill
Electric discharge is 3.0-4.2V by voltage.
Lithium deposition feelings of the graphitized carbon fibre electrode of embodiment 2 after first week charging are observed by scanning electron microscope
Condition.It is the results show that lithium metal is deposited in the three-dimensional framework of graphitized carbon fibre electrode, and does not have lithium metal branch outside skeleton
Crystalline substance is formed.
Lithium deposition feelings of the graphitized carbon fibre electrode of embodiment 2 after circulation 30 weeks are observed by scanning electron microscope
Condition.It is the results show that lithium metal is still controllable is deposited in three-dimensional framework after circulation 30 weeks, and without gold outside skeleton
Belong to Li dendrite.
Dissolution lithium feelings of the graphitized carbon fibre electrode of embodiment 2 after circulation 30 weeks are observed by scanning electron microscope
Condition.It is substantially residual without lithium metal the results show that very clean inside graphitized carbon fibre surface and three-dimensional framework after lithium dissolution
Remaining, this illustrates the basic completely reversibility dissolution of lithium metal.
2 loop test of embodiment after 30 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency keep
97.5%.
Embodiment 3
The present embodiment is for illustrating electrode of the present invention and its preparation method and application.
1. the carbon nanocoils three-dimensional structure electrode that production is used for lithium secondary battery
The carbon nanocoils piece of commercialization is washed into the disk that diameter is 14mm, with a thickness of 2 μm.Wherein, carbon nanocoils is straight
Diameter is 70nm, and the ratio of amorphous carbon and graphitic carbon is (according to the representative amorphous carbon in respective material Raman spectrum in material
The peak D and the integral area at the peak G for representing graphitic carbon calculate) it is 0.65.
As shown in fig. 6, obtained carbon nanocoils electrode has three-dimensional structure, porosity 92%.
Above-mentioned carbon nanocoils electrode is used into dilute hydrochloric acid, deionized water and alcohol washes respectively, then receives the carbon after cleaning
Rice noodles electrode is placed on room temperature pumping 12h in vacuum warehouse and makes it dry.
2. lithium metal secondary battery
Using carbon nanocoils electrode manufactured in the present embodiment as cathode, with LiCoO2For positive electrode, use concentration for
The LiPF of 1molL-16The solution for being dissolved in ethylene carbonate (EC) and dimethyl carbonate (DMC) (volume ratio 1:1) is electrolyte,
Assembling obtains lithium metal secondary battery.
3. lithium metal secondary battery electro-chemical test
Constant current charge-discharge test is carried out to full battery, wherein test temperature is 25 DEG C, and current density 20mAg-1 fills
Electric discharge is 3.0-4.2V by voltage.
Lithium deposition situation of the carbon nanocoils electrode of embodiment 3 after first week charging is observed by scanning electron microscope.
It is the results show that lithium metal is deposited in the three-dimensional framework of carbon nanocoils electrode, and is formed outside skeleton without metal Li dendrite.
The electron scanning micrograph of lithium deposition of the carbon nanocoils electrode of the embodiment after circulation 30 weeks show,
Lithium metal is still controllable after recycling 30 weeks is deposited in skeleton, and does not have metal Li dendrite outside skeleton.After recycling 30 weeks
Lithium dissolution electron scanning micrograph show, lithium dissolve out after carbon nanocoils surface and skeletal internal it is very clean, base
, without lithium metal remnants, this illustrates the basic completely reversibility dissolution of lithium metal for this.
3 loop test of embodiment after 50 weeks charging/discharging voltage it is still highly stable, and polarize it is very small, coulombic efficiency keep
98.5%.
Embodiment 4
The present embodiment is for illustrating electrode of the present invention and its preparation method and application.
1. the gold-plated carbon fiber three-dimensional structure electrode that production is used for lithium secondary battery
The carbon cloth of commercialization is washed into the disk that diameter is 14mm, with a thickness of 3 μm.Wherein, the diameter of carbon fiber is
700nm, the ratio of amorphous carbon and graphitic carbon is (according to the peak D of the representative amorphous carbon in respective material Raman spectrum in material
Calculated with the integral area at the peak G for representing graphitic carbon) it is 0.68.Show that carbon cloth has by electron scanning micrograph
Three-dimensional structure, porosity 89%.Above-mentioned carbon fiber electrode is used into citric acid, deionized water and alcohol washes respectively, then
Carbon fiber electrode after cleaning is placed on room temperature pumping 12h in vacuum warehouse to make it dry.Pass through the carbon fiber of sputtering method after the drying
It ties up and deposits one layer of gold particle (i.e. coating) on electrode surface, with a thickness of 5nm.
2. lithium metal secondary battery
Using gold-plated carbon fiber electrode manufactured in the present embodiment as cathode, with LiCoO2For positive electrode, use concentration for
1mol·L-1LiPF6The solution for being dissolved in ethylene carbonate (EC) and dimethyl carbonate (DMC) (volume ratio 1:1) is electrolyte,
Assembling obtains lithium metal secondary battery.
3. lithium metal secondary battery electro-chemical test
Lithium metal secondary battery is tested using method identical with Examples 1 and 2.The gold-plated carbon fiber of the embodiment
The electron scanning micrograph of lithium deposition of the dimension electrode after circulation 30 weeks shows that lithium metal is still controllable after circulation 30 weeks
Be deposited in skeleton, and do not occur metal Li dendrite outside skeleton.The scanning electron of lithium dissolution after recycling 30 weeks is aobvious
Micro mirror photo is shown, very clean inside the combination electrode surface and pit after lithium dissolution, substantially without lithium metal remnants, this explanation
The basic completely reversibility dissolution of lithium metal.Charge and discharge cycles curve shows that the lithium metal secondary battery is after circulation 100 weeks, capacity
Conservation rate is 99.1%.
Embodiment 5
The present embodiment is for illustrating electrode of the present invention and its preparation method and application.
1. the carbon nanotube three-dimensional structure electrode that production 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 2 μm.Wherein, carbon nanotube
Internal diameter is 20nm, outer diameter 40nm, and the ratio of amorphous carbon and graphitic carbon is (according in respective material Raman spectrum in material
The integral area for representing the peak D of amorphous carbon and representing the peak G of graphitic carbon calculates) it is 0.74.It is shone by scanning electron microscope
Piece shows that carbon nanotube has three-dimensional structure, porosity 95%.By above-mentioned carbon nanotube sponge electrode use respectively dilute hydrochloric acid,
Deionized water and alcohol washes, the carbon nanotube sponge electrode after cleaning, which is then placed on room temperature pumping 12h in vacuum warehouse, makes it
It is dry.
2. assembling metal sodium rechargeable battery
It is anode with vanadium phosphate sodium, using 1molL using carbon nanotube sponge electrode manufactured in the present embodiment as cathode-1
NaPF6The mixed solution for being dissolved in ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio 1:1) is electrolyte, assembling
Obtain metal sodium rechargeable battery.
3. metallic sodium secondary cell electro-chemical test
It in the present embodiment, is safety, the cycle life of testing the cathode, with carbon nanotube sea manufactured in the present embodiment
Continuous electrode is cathode, is to test the electrochemistry of the electrode using above-mentioned electrolyte assembled battery to electrode with vanadium phosphate sodium
Energy.Wherein, test temperature is 25 DEG C, current density 20mAg-1, charging/discharging voltage range is 2.0-4.0V.
The electron scanning micrograph of deposition sodium of the carbon nanotube sponge electrode of the embodiment after circulation 30 weeks is aobvious
Show, metallic sodium is still controllable after circulation 30 weeks is deposited in skeleton, and does not occur metallic sodium dendrite outside skeleton.It follows
The electron scanning micrograph of sodium dissolution after ring 30 weeks shows that the electrode surface and skeletal internal after sodium dissolution are very dry
Only, substantially without metallic sodium remnants, this illustrates metallic sodium substantially completely reversible dissolution.Charge and discharge cycles curve shows, the metallic sodium
Secondary cell is after circulation 100 weeks, capacity retention ratio 96.7%.
Embodiment 6
The present embodiment is for illustrating electrode of the present invention and its preparation method and application.
1. the carbon fiber three-dimensional structure electrode that production is used for all solid lithium secondary battery
The carbon cloth of commercialization is washed into the disk that diameter is 14mm, with a thickness of 3 μm.Wherein, the diameter of carbon fiber is
700nm, the ratio of amorphous carbon and graphitic carbon is (according to the peak D of the representative amorphous carbon in respective material Raman spectrum in material
Calculated with the integral area at the peak G for representing graphitic carbon) it is 0.68.Show that carbon cloth has by electron scanning micrograph
Three-dimensional structure, porosity 89%.Above-mentioned carbon fiber electrode is used into citric acid, deionized water and alcohol washes respectively, then
Carbon pricker dimension electrode after cleaning is placed on room temperature pumping 12h in vacuum warehouse to make it dry.
2. all-solid-state battery
It is anode with cobalt acid lithium, using Li using carbon fiber electrode manufactured in the present embodiment as cathode10GeP2S12It is all solid state
Electrolyte, assembling obtain all-solid-state battery, test the chemical property of the carbon fiber electrode.Wherein, test temperature is 25 DEG C, is filled
Discharge current density is 10mAg-1, charging/discharging voltage range is 2.0-4.5V.
The electron scanning micrograph of lithium deposition of the carbon fiber electrode of the embodiment after circulation 30 weeks is shown, is being followed
Lithium metal is still controllable after ring 30 weeks is deposited in three-dimensional framework, and does not have metal Li dendrite outside skeleton.Circulation 30 weeks
The electron scanning micrograph of lithium dissolution afterwards shows that the carbon pricker dimension table face and skeletal internal after lithium dissolution are very clean, base
, without lithium metal remnants, this illustrates the basic completely reversibility dissolution of lithium metal for this.Charge and discharge cycles curve shows that the all-solid-state battery exists
After recycling 100 weeks, capacity retention ratio 98.5%.
Embodiment 7
The present embodiment is for illustrating electrode of the present invention and its preparation method and application.
1. the carbon nanotube three-dimensional structure electrode that production is used for Mg secondary cell
The carbon nanotube paper of commercialization is washed into the disk that diameter is 14mm, with a thickness of 1 μm.Wherein, carbon nanotube is interior
Diameter is 20nm, outer diameter 40nm, and the ratio of amorphous carbon and graphitic carbon is (according to the generation in respective material Raman spectrum in material
The peak D of table amorphous carbon and the integral area at the peak G for representing graphitic carbon calculate) it is 0.82.
As shown in fig. 7, obtained carbon nanotube paper electrode has three-dimensional structure, diameter is 20~40nm, porosity
It is 85%.Above-mentioned carbon nanotube paper electrode is used into dilute hydrochloric acid, deionized water and alcohol washes respectively, then receives the carbon after cleaning
Mitron paper electrode is placed on room temperature pumping 12h in vacuum warehouse and makes it dry.
2. assembling metal Mg secondary cell
Carbon nanotube paper electrode manufactured in the present embodiment is negative pole, MgCoSiO4For anode of magnesium ion battery material, with
0.25mol·L-1Mg (AlCl2EtBu)2/ THF is that electrolyte assembles to obtain metal Mg secondary cell, tests the electricity of the electrode
Chemical property.Wherein, test temperature is 25 DEG C, current density 30mAg-1, charging/discharging voltage range is 0.5-2.1V.
The electron scanning micrograph of deposition magnesium of the carbon nanotube paper electrode of the embodiment after circulation 30 weeks show,
Magnesium metal is still controllable after circulation 30 weeks is deposited in skeleton, and does not have magnesium metal dendrite outside skeleton.Circulation 30 weeks
The electron scanning micrograph of magnesium dissolution afterwards shows that the carbon nano tube surface and skeletal internal after magnesium dissolution are very clean,
Substantially without magnesium metal remnants, this illustrates magnesium metal substantially completely reversible dissolution.Charge and discharge cycles curve shows that the magnesium metal is secondary
Battery is after circulation 100 weeks, capacity retention ratio 98.1%.
Embodiment 8
The present embodiment is for illustrating electrode of the present invention and its preparation method and application.
1. the carbon nanocoils three-dimensional structure electrode that production is used for potassium secondary cell
The carbon nanocoils paper of commercialization is washed into the disk that diameter is 14mm, with a thickness of 1.5 μm, amorphous carbon in material
With the ratio of graphitic carbon (according to the representative amorphous carbon in respective material Raman spectrum the peak D and represent the peak G of graphitic carbon
Integral area calculates) it is 0.58.Show that carbon nanocoils paper has three-dimensional structure, porosity by electron scanning micrograph
It is 90%.Above-mentioned carbon nanocoils paper electrode is used into dilute hydrochloric acid, deionized water and alcohol washes respectively, then receives the carbon after cleaning
Rice noodles paper electrode is placed on room temperature pumping 12h in vacuum warehouse and makes it dry.
2. assembling metallic potassium secondary cell
Using the carbon nanocoils paper electrode prepared in the present embodiment as cathode, with K3V2(PO4)2F3For anode, using 1mol
The KPF of L-16The mixed solution for being dissolved in ethylene carbonate (EC) and propene carbonate (PC) (volume ratio 1:1) is electrolyte, assembling
Obtain metallic potassium secondary cell.
3. metallic potassium secondary cell electro-chemical test
It in the present embodiment, is safety, the cycle life of testing the cathode, with carbon nanocoils paper manufactured in the present embodiment
Electrode is cathode, with K3V2(PO4)2F3To test the electrochemistry of the electrode using above-mentioned electrolyte assembled battery to electrode
Energy.Wherein, test temperature is 25 DEG C, current density 20mAg-1, charging/discharging voltage range is 2.0-4.5V.
The electron scanning micrograph of deposition sodium of the carbon nanocoils paper electrode of the embodiment after circulation 30 weeks show,
Metallic sodium is still controllable after circulation 30 weeks is deposited in skeleton, and does not occur metallic potassium dendrite outside skeleton.Circulation
The electron scanning micrograph of potassium dissolution after 30 weeks shows that the electrode surface and skeletal internal after potassium dissolution are very clean,
Substantially without metallic potassium remnants, this illustrates metallic potassium substantially completely reversible dissolution.Charge and discharge cycles curve shows that the metallic potassium is secondary
Battery is after circulation 80 weeks, capacity retention ratio 97.3%.
Embodiment 9
The present embodiment is for illustrating electrode of the present invention and its preparation method and application.
1. the carbon nanotube three-dimensional structure electrode that production is used for MH secondary battery
By the carbon nanotube paper of commercialization be washed into diameter be 14mm disk, with a thickness of 1.5 μm, in material amorphous carbon and
The ratio of graphitic carbon is (according to the product at the peak D and the peak G for representing graphitic carbon of the representative amorphous carbon in respective material Raman spectrum
Divide areal calculation) it is 0.82.Show that carbon nanotube paper has three-dimensional structure by electron scanning micrograph, porosity is
88%.
Above-mentioned carbon nanotube paper electrode is used into dilute hydrochloric acid, deionized water and alcohol washes respectively, then by the carbon after cleaning
Nanotube paper electrode is placed on room temperature pumping 12h in vacuum warehouse and makes it dry.
2. assembling metal MH secondary battery
It is negative pole with carbon nanotube paper electrode manufactured in the present embodiment, with MnO2For Zinc ion battery positive electrode, use
1mol·L-1ZnSO4Aqueous solution be electrolyte, assembling obtain metal MH secondary battery, test the electrochemistry of the electrode
Energy.Wherein, test temperature is 25 DEG C, current density 30mAg-1, voltage range 0.8-2.0V.
The electron scanning micrograph of deposition zinc of the carbon nanotube paper electrode of the embodiment after circulation 30 weeks show,
Metallic zinc is still controllable after circulation 30 weeks is deposited in three skeletons, and does not have metal zinc dendrite outside skeleton.Circulation
The electron scanning micrograph of zinc dissolution after 30 weeks shows that the carbon nano tube surface and skeletal internal after zinc dissolution are very dry
Only, substantially without metallic zinc remnants, this illustrates metallic zinc substantially completely reversible dissolution.Charge and discharge cycles curve shows, the metallic zinc
Secondary cell is after circulation 100 weeks, capacity retention ratio 98.6%.
Embodiment 10
The present embodiment is for illustrating electrode of the present invention and its preparation method and application.
1. production is used for aluminium-air secondary battery carbon nanotube three-dimensional structure aluminium electrode
By the carbon nanotube paper of commercialization be washed into diameter be 14mm disk, with a thickness of 1.5 μm, in material amorphous carbon and
The ratio of graphitic carbon is (according to the product at the peak D and the peak G for representing graphitic carbon of the representative amorphous carbon in respective material Raman spectrum
Divide areal calculation) it is 0.82.Show that carbon nanotube paper has three-dimensional structure by electron scanning micrograph, porosity is
88%.Above-mentioned carbon nanotube paper electrode is used into dilute hydrochloric acid, deionized water and alcohol washes respectively, then by the carbon nanometer after cleaning
Pipe paper electrode is placed on room temperature pumping 12h in vacuum warehouse and makes it dry.
By depositing one layer of aluminum metal (i.e. coating), thickness on the carbon nanotube paper electrode surface of vapour deposition method after the drying
For 10nm, it is prepared into carbon nanotube three-dimensional structure metal aluminium electrode.
2. assembling aluminium-air secondary battery
It is positive oxygen with graphene film using carbon nanotube three-dimensional structure metal aluminium electrode manufactured in the present embodiment as cathode
The carrier of gas, with 0.1molL-1KOH solution be electrolyte assemble to obtain aluminium-air secondary battery.Wherein, test temperature is
25 DEG C, control discharge capacity is 0.5mAh.
The scanning electron of deposition of aluminum of the carbon nanotube three-dimensional structure metal aluminium electrode of the embodiment after circulation 10 weeks is aobvious
Micro mirror photo shows that metallic aluminium is still controllable after circulation 10 weeks is deposited in carbon skeleton, and does not have metal outside skeleton
Aluminium dendrite.Charge and discharge cycles curve shows that the aluminium-air secondary battery is after circulation 50 weeks, capacity retention ratio 95.2%.
Comparative example 1
In comparative example 1, using pure copper foil as cathode, with LiCoO2For anode, use concentration for 1molL-1LiPF6It is molten
It is electrolyte in the solution of ethylene carbonate (EC) and dimethyl carbonate (DMC) (volume ratio 1:1), is assembled into the secondary electricity of lithium metal
Pond.Constant current charge-discharge test is carried out to the battery, wherein test temperature is 25 DEG C, current density 20mAcm-1。
The lithium deposition electron scanning micrograph of copper electrode after first week charging shows that copper foil surface is paved with mixed and disorderly gold
Belong to Li dendrite；Charging/discharging voltage curve is unstable in cyclic process as the result is shown for electrochemistry cycle performance, after 50 weeks circulations, coulomb
Efficiency is only 71.9%.
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 three-dimensional structure electrode, which is characterized in that the electrode includes carbon material three-dimensional framework and is attached to three-dimensional bone
Electroactive substance on frame；
Preferably, the carbon material is selected from one or more of: carbon nanotube, carbon nanocoils, carbon fiber.
2. electrode according to claim 1, which is characterized in that the carbon material three-dimensional framework with a thickness of 1 μm~1000 μ
M, preferably 5~100 μm, more preferably 10~50 μm；And/or
When on the carbon material three-dimensional framework without electroactive substance, porosity is 50%~99%, preferably 60%
~95%.
3. electrode according to claim 1 or 2, which is characterized in that the pipeline diameter of the carbon material be 20nm~
10000nm, preferably 20nm~5000nm；
The length of the carbon material is 10~10000, preferably 100~2000；And/or
The ratio of amorphous carbon and graphitic carbon is 0.2~5.0, preferably 0.5~2.0 in the carbon material.
4. electrode according to any one of claim 1 to 3, which is characterized in that the carbon material three-dimensional framework includes carbon
The substrate and the coating formed by metal that material three-dimensional skeleton is formed；
Preferably, the material one or more of of the coating: iron, gold, silver, copper, titanium, aluminium, nickel, iron, preferably iron, copper,
Nickel, titanium；
It is highly preferred that the coating with a thickness of 0~50nm, preferably 0~10nm.
5. electrode according to any one of claim 1 to 4, which is characterized in that the carbon three-dimensional structure electrode includes certainly
Brace type electrode and coated in the electrode on other metal foils；
Preferably, the material of the metal foil is selected from one or more of: iron, gold, copper, aluminium, titanium, nickel, stainless steel, preferably
For iron, copper, aluminium, titanium, nickel, stainless steel.
6. electrode according to any one of claim 1 to 6, which is characterized in that the electroactive substance is electrification
Learn active metal and/or its alloy；
Preferably, the alloy is selected from the alloy that electroactive metal and electrochemically inactive material are constituted, activity in alloy
The total atom percentage composition of metallic element is not less than 20%；
It is highly preferred that the electroactive metal is selected from one or more of: lithium, sodium, potassium, magnesium, aluminium, zinc；
The electrochemically inactive material be selected from one or more of: boron, carbon, nitrogen, magnesium, aluminium, silicon, phosphorus, sulphur, titanium, manganese, iron,
Nickel, copper, zinc, silver, tin.
7. the preparation method of electrode according to any one of claim 1 to 6, which is characterized in that the described method includes:
Electroactive substance is filled in the carbon material three-dimensional framework；
Preferably, the fill method is selected from one or more of: electrochemical deposition, chemical plating, sputtering sedimentation, vapor deposition.
8. a kind of battery, which is characterized in that the battery includes carbon three-dimensional structure electricity described in any one of claims 1 to 6
Carbon three-dimensional structure electrode made from pole or preparation method according to claim 7.
9. battery according to claim 8, which is characterized in that the battery is secondary cell；Preferably, the battery choosing
From one or more of: serondary lithium battery, lithium-sulfur cell, lithium-air battery；Secondary sode cell, sodium-sulfur battery, sodium-sky
Pneumoelectric pond；Zinc-air battery, secondary potassium battery, secondary Mg battery, secondary aluminium cell, zinc-manganese dioxide secondary cell, and
The secondary potassium battery of the secondary sode cell of solid/semi-solid serondary lithium battery, solid/semi-solid, solid/semi-solid, solid/semi-solid
Secondary Mg battery, solid/semi-solid secondary aluminium cell.
10. battery according to claim 8 or claim 9, which is characterized in that the battery includes anode, the carbon three-dimensional structure
Electrode is cathode and the solid-state or semisolid or gel state or liquid electrolyte that are placed between positive and negative electrode.
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| CN114930572A (en) * | 2020-11-10 | 2022-08-19 | 株式会社Lg新能源 | Negative electrode for all-solid battery and all-solid battery including the same |
| EP4084126A4 (en) * | 2020-11-10 | 2023-11-08 | LG Energy Solution, Ltd. | Anode for all-solid-state battery and all-solid-state battery including same |
| CN113644267A (en) * | 2021-08-03 | 2021-11-12 | 西北工业大学 | Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof |
| CN113644267B (en) * | 2021-08-03 | 2023-09-29 | 西北工业大学 | Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof |
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