CN106299246B - Metal secondary batteries composite negative pole and its application - Google Patents
Metal secondary batteries composite negative pole and its application Download PDFInfo
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- CN106299246B CN106299246B CN201610835690.1A CN201610835690A CN106299246B CN 106299246 B CN106299246 B CN 106299246B CN 201610835690 A CN201610835690 A CN 201610835690A CN 106299246 B CN106299246 B CN 106299246B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of metal secondary batteries composite negative pole and preparation methods, compared to direct carried metal smooth copper foil as metal secondary batteries cathode, the metal secondary batteries composite negative pole has high capacity, long-life, the advantages that stable circulation, simultaneously, the carrier material that the composite negative pole includes is low in cost, metal secondary batteries composite negative pole preparation process based on the carrier material is simple, it can satisfy high-energy density using the metal secondary batteries of the secondary cell composite negative pole, long-life, the conditions such as safety and stability, and it is expected to be applied in high-energy density device, it is with a wide range of applications.
Description
Technical field:
The invention belongs to field of electrochemical power source, and in particular to a kind of metal secondary batteries composite negative pole and preparation method,
High capacity, long-life, the metal secondary batteries of safety based on the composite negative pole and its answering in high-energy density power supply system
With.
Background technique:
In recent years, with the popularization of the energy storage systems such as electric car, smart grid, people are for high-energy density secondary electricity
The demand of pond body system is further urgent.
Metal secondary batteries system is a kind of secondary cell body using metals such as lithium, sodium, magnesium directly as battery cathode
System has the theoretical energy density considerably beyond conventional lithium ion battery, and by taking lithium-sulfur rechargeable battery as an example, theoretical energy density is high
Up to 2654wh/kg, and the actual energy density of 500-600wh/kg is even likely to be breached in coming years in a period of time.Due to
The high-energy density of metal secondary batteries makes it be expected to become next-generation energy storage device and is applied to smart grid, electronic vapour
In the energy storage devices such as vehicle.
Currently, the main problem that metal negative electrode faces in metal secondary batteries is: (1) non-homogeneous heavy on metal negative electrode surface
Dendrite pierces through diaphragm and causes cell safety problem brought by battery short circuit during dendrite caused by product and following cycle；
(2) in cyclic process, constantly the metal surface of exposure in the electrolytic solution is reacted with electrolyte contacts leads to battery coulombic efficiency
Low problem；Therefore, the application of metal negative electrode must effectively solve above-mentioned two problems.
Currently, can be improved effectively to solve the problems, such as that dendrite and coulombic efficiency are low by the way that additive is added in electrolyte
Coulombic efficiency (such as Nat Commun, 2015.6:p.7436.), this method cannot fundamentally solve metal negative electrode and be circulated throughout
In journey repeatedly with electrolyte contacts and react, be unsuitable for long-life batteries system；Or by between metal negative electrode and diaphragm
Increase artificial protective layer can effectively dendrite inhibition growth (such as patent CN104966814A, CN104617259A,
CN105280886A), but this method preparation condition is more demanding and process is cumbersome, is unsuitable for being mass produced and apply, separately
Outer modification cathode unavoidably will increase cathode weight, to reduce cathode specific capacity.Therefore, high capacity, safety, circulation are prepared
The metal negative electrode of service life length is for constructing high-energy, long-life, safe and reliable metal secondary batteries system important in inhibiting.
Currently, preparing composition metal second electrode by design, there are reports, and patent CN104716330A is prepared for
Three-dimensional porous collector is used for carried metal cathode as metal secondary batteries cathode, but this method preparation process is more numerous
It is trivial, and suitable content of metal is lower；Patent CN105374991A preparation compound carbon skeleton microsphere diameter be 100 μm with
Interior, within 50nm, above-mentioned condition and this patent protection content are entirely different in aperture；Patent CN104466095A prepares complex lithium
The used heat pressing process of foil is different from the preparation method that this patent is related to, and two above patent is limited to preparation method and only fits
For cathode of lithium；Although patent CN101043077A and this patent are using similar material, above-mentioned patent uses the material
The performance of sodium polysulfide/bromine battery is improved with carrying transition metal as conductive substrates.
Summary of the invention:
The present invention provides a kind of metal secondary batteries composite negative pole, which has specific capacity height, coulomb
It is high-efficient, voltage polarizing is small, the advantages that having extended cycle life, key is after multiple cyclic process, the cathode and passes through phase
Compared with the metal negative electrode (such as lithium, sodium, magnesium) of condition preparation, the coulombic efficiency during circulating battery can be effectively improved, and
And generated without obvious dendrite, to increase the service life of battery.Meanwhile the carrier material in the composite negative pole including is low in cost,
Metal composite negative pole preparation process based on the carrier material is simple, and using the composite negative pole can to avoid using collector,
To improve the specific discharge capacity of electrode indirectly.Therefore the invention has the potentiality of practical application.
Present invention firstly provides a kind of metal secondary batteries composite negative poles, are made of carrier material and carried metal, described
Metal refers to that, directly using one or more of lithium metal, sodium, magnesium, the carrier material is made of carbon fiber, fiber
Diameter is 10-50 μm, and the specific surface area of carrier material is 100-600m2/ g, Kong Rongwei 0.2-8cm3/ g, average pore size 0.05-
400 μm, carrier material is with a thickness of 0.5-5mm, it is preferable that the diameter of the fiber is 20-40 μm, and the specific surface area is 300-
600m2/ g, Kong Rongwei 6-8cm3/ g, average pore size are 50-100 μm, and carrier material is with a thickness of 0.8-1.2mm.It is preferred that the load
Body material is without chemical surface treatment, for example, handling without alkaline reagent.
It is further preferred that the carrier material is graphite felt, carbon cloth, three-dimensional net structure is formed by carbon fiber.
The present invention further provides the preparation methods of above-mentioned metal secondary batteries composite negative pole, and lithium metal, sodium, magnesium are passed through
Electrochemical deposition, melting infiltration etc. are either physically or chemically carried in the carrier material, preferably electrochemical deposition method.
It is further preferred that metal (such as lithium, sodium, magnesium) is anode, in 0.1-4mA/cm using carrier material as cathode2's
Under current density, in deposited on supports 2-20mAh/cm2Metal simple-substance, it is preferable that the current density be 0.5-2mAh/
cm2, deposition 3-10mAh/cm2, it is highly preferred that the current density is 0.5-1mAh/cm2, deposition 6-8mAh/
cm2。
It is further preferred that metal (such as lithium, sodium, magnesium) and carrier material to be placed in inert atmosphere and be warming up to 180-500
DEG C, 1-5h is calcined, penetrates into metal in carrier material, it is preferable that the calcination temperature is 200-450 DEG C, and calcination time is
2-3h。
The present invention further provides a kind of metal secondary batteries, are made using metal composite negative pole prepared by above-mentioned preparation method
For battery cathode.
The present invention further provides the metal secondary batteries for the cathode for using above-mentioned cathode or above-mentioned preparation method to prepare
In high-energy density, have extended cycle life, the application in the energy storage device of safety and stability.
The carrier material is used to prepare metal secondary batteries cathode and has the advantage that (1) Large ratio surface --- can have
Effect reduces current density, enables metal in its surface uniform load；(2) macropore holds --- represent material theory with higher
Load capacity；(3) electric conductivity is good --- guarantee that material is capable of providing good conductive network；Three above advantage is in theory
The bright material is suitable for the preparation of metal secondary batteries cathode.
A kind of metal secondary batteries assembled using above-mentioned metal secondary batteries composite negative pole, wherein metal secondary batteries are multiple
Closing cathode can be improved coulombic efficiency, increase cycle life and safety, the metal secondary batteries refer to using lithium metal,
One of sodium, magnesium etc. or a variety of secondary cell systems as cathode.
The high-energy density that is assembled using the metal composite negative pole material is had extended cycle life, the metal two of safety and stability
Application of the primary cell in energy storage device, similarly belongs to the scope of protection of the present invention.
Detailed description of the invention:
Fig. 1 is the electron scanning micrograph of graphite felt.
Fig. 2 is the raman spectrum of graphite felt.
Fig. 3 is that graphite felt loads 8mAh/cm in embodiment 12Electron scanning micrograph after lithium metal.
Fig. 4 is that graphite felt loads 8mAh/cm in embodiment 12Electron scanning micrograph after 5 circle of lithium metal circulation.
Fig. 5 is embodiment 1 in 1mA/cm2The constant current charge-discharge curve graph of 35th circle circulation under current density condition.
Fig. 6 is the electron scanning micrograph of common copper foil in comparative example 1.
Fig. 7 is that copper foil loads 8mAh/cm in comparative example 12Electron scanning micrograph after lithium metal.
Fig. 8 is that copper foil loads 8mAh/cm in comparative example 12Electron scanning micrograph after 5 circle of lithium metal circulation.
Fig. 9 is circulation-coulombic efficiency comparison diagram in embodiment 1 and comparative example 1.
Specific embodiment:
The present invention is further explained in the light of specific embodiments.
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material
It obtains from commercial channels.
Embodiment 1:
(1) processing of graphite felt carrier
Graphite felt used in experiment (being purchased from Beijing graphite factory) is made of carbon fiber, and carbon fiber diameter is as seen from Figure 1
10 μm, measure graphite felt materials unit mass specific surface area 454m2/ g, it is 6.4cm that unit mass hole, which holds,3/ g, average pore size are
100 μm, thickness is about 1mm, quality 5.7mg.Fig. 2 is the raman spectrum of graphite felt, IG/ID=1.16.
Graphite felt is washed into the electrode slice size of Φ=10mm, made graphite felt electrode is several with dehydrated alcohol flushing
Secondary, until clean, drying is stand-by.
(2) the lithium metal composite negative pole based on graphite felt is prepared
Using graphite felt materials as cathode, metal lithium sheet is anode, in 1.1mA/cm2Current density under, pass through electrochemistry
The method of deposition loads 8mAh/cm in graphite felt hole2Lithium metal.
By in the electron micrograph of Fig. 3 it can be seen that carried metal lithium after, lithium metal be distributed in graphite felt hole and
Surface, a large amount of lithium metal deposition do not cause apparent Li dendrite.
(3) lithium metal secondary battery is assembled with above-mentioned composite negative pole
The secondary electricity of lithium metal is can be obtained into the lithium anode of above-mentioned preparation and anode appropriate, electrolyte, diaphragm assembling
Pond.
In the present embodiment, for properties such as coulombic efficiency, the cyclical stabilities of testing the cathode, still with lithium piece be to electrode,
And lithium metal secondary battery is assembled using above-mentioned electrolyte, diaphragm.
(4) lithium metal secondary battery electrochemical properties are tested
Using blue electric battery test system to above-mentioned lithium metal secondary battery in 1mA/cm2It is carried out under current density condition permanent
Charge-discharge test is flowed, Fig. 4 is the electron micrograph on graphite felt surface after circulating battery 5 encloses, stone after recycling as seen from the figure
The lithium of black felt electrode surface deposition is more uniform, occurs without apparent Li dendrite.Fig. 5 is the constant current charge-discharge of the 35th circle circulation
Figure, it may be said that it is bright after 500 hours circulations battery it is still stable, and polarize it is smaller.By calculating, 8mAh/cm is loaded2
Lithium anode afterwards has the reversible specific discharge capacity of 1100mAh/g.
Fig. 9 is that graphite felt loads the secondary cell composite negative pole of lithium and the secondary battery negative pole cycle efficieny of copper foil load lithium
Comparison diagram, the secondary battery negative pole of copper foil load lithium cycle efficieny in 15 circle fluctuate, and subsequently result in battery short circuit, and stone
The secondary battery negative pole of black felt load lithium is still able to maintain 98% or so coulomb effect after 47 circle circulations (being up to 750 hours)
Rate.
Embodiment 2:
Difference from Example 1 is that the thickness of graphite felt carrier is about 3mm, and electrode tablet quality is 13.9mg, is used for
Electrochemical deposition of metal lithium.After tested, 8mAh/cm is loaded2Lithium anode afterwards has the reversible specific capacity of 450mAh/g.
Embodiment 3:
Difference from Example 1 is lithium metal deposition, and the combination electrode in the present embodiment in graphite felt by carrying
16mAh/cm is deposited in body2Lithium metal, by test, load 16mAh/cm2Lithium anode with 2200mAh/g can
Inverse specific capacity.
Embodiment 4:
Difference from Example 1 is to prepare the metallic sodium cathode based on graphite felt carrier, similarly, with graphite felt material
Material is cathode, and metallic sodium piece is anode, by the method for electrochemical deposition in graphite felt supported on carriers 8mAh/cm2Metal
Sodium.
Embodiment 5:
Difference from Example 1 is to prepare the magnesium metal cathode based on graphite felt carrier, similarly, with graphite felt material
Material is cathode, and metal magnesium sheet is anode, by the method for electrochemical deposition in graphite felt supported on carriers 8mAh/cm2Metal
Magnesium.
Embodiment 6:
Difference from Example 1 is that lithium metal is carried in graphite felt carrier using the method for melting infiltration.
Lithium metal ingot is put on the graphite felt pole piece substituted the bad for the good, is heated to 450 DEG C, calcining at constant temperature 2h in an inert atmosphere,
It is tested after natural cooling for assembling lithium metal secondary battery.
Embodiment 7:
Difference from Example 6 is that process of osmosis is melted under inert atmosphere is heated to 200 DEG C, calcining at constant temperature 2h, to
It is tested after natural cooling for lithium metal secondary battery.
Embodiment 8:
Difference from Example 1 is using carbon cloth as carrier material for deposited metal lithium.Carbon cloth unit mass
Specific surface area 454m2/ g, it is 2.5cm that unit mass hole, which holds,3/g.Similarly, using carbon cloth as cathode, metal lithium sheet is anode, is passed through
The method of electrochemical deposition is by 8mAh/cm2Lithium metal be carried on carbon cloth, and for lithium metal secondary battery test.
Comparative example 1:
Other conditions are same as Example 1, the difference is that 8mAh/cm will be loaded2The copper foil of lithium metal is as two
Primary cell cathode, later again using lithium metal as to electrode and the secondary battery negative pole be assembled into full battery test surfaces pattern and
The cycle performance of the cathode.
Fig. 6 is smooth copper foil surface electron scanning micrograph；Fig. 7 is the scanning electron of the copper foil surface after deposition
Microscope photo, it can be found that there is copper foil surface intensive fibrous metal lithium to exist from figure；Fig. 8 be modification cathode of lithium with
Lithium metal to electrode assembling at lithium metal secondary battery circulation 5 circle after modify cathode of lithium surface stereoscan photograph, by scheming
As it can be seen that by 5 circle circulation after electrode surface by largely can not reversion products cover, this will seriously affect cathode coulomb effect
Rate and cycle life.
Comparative example 2:
Other conditions are same as Example 1, the difference is that loading 25mAh/cm in graphite felt carrier material2's
Lithium metal is equally tested using lithium metal as being assembled into full battery with the secondary battery negative pole to electrode later.
Comparative example 3:
Difference from Example 1 is that graphite felt, which is carried out 1mol/L potassium hydroxide solution, first is activated 5h, with
Increase graphite felt materials specific surface area.Graphite felt materials unit mass specific surface area is 834m after measuring activation2/ g, unit mass
Kong Rongwei 2.9cm3/g.Similarly, using the graphite felt after activating as cathode, metal lithium sheet is anode, passes through electrochemical deposition
Method is by 8mAh/cm2Lithium metal be carried on carbon cloth, and for lithium metal secondary battery test.
The performance test table of table 1 embodiment 1-8 and comparative example 1-2
Wherein, specific capacity is calculated based on the quality of carrier material or copper foil, and coulombic efficiency is after stable circulation
Coulombic efficiency.
In conclusion the metal secondary batteries composite negative pole after graphite felt load lithium has high capacity, long-life, circulation steady
The advantages that determining can satisfy high-energy density, long-life, safety surely using the metal secondary batteries of the secondary cell composite negative pole
Fixed wait requires.Meanwhile the secondary cell composite negative pole is low in cost, preparation process is simple, is suitable for practical application and production.Cause
This, the metal secondary batteries that the metal composite negative pole provided by the present invention based on graphite felt carrier is prepared are expected in high energy
It is applied, is with a wide range of applications in metric density device.
It is not intended to limit the present invention finally, it is stated that above embodiments are merely to illustrate specific embodiment, this field
Those of ordinary skill's main contents according to the present invention and design can carry out easy accommodation or equivalent replacement, therefore this hair
Bright protection scope should be subject to protection scope described in claims.
Claims (3)
1. a kind of metal secondary batteries composite negative pole material, is made of carrier material and carried metal, the metal is lithium metal,
It is characterized in that, the carrier material is the graphite felt being made of carbon fiber, the diameter of fiber is 10-50 μm, carrier material
Specific surface area is 100-600m2/ g, Kong Rongwei 6-8cm3/ g, average pore size are 50-100 μm, and carrier material is with a thickness of 0.8-
1.2mm, and the lithium metal is carried on carrier material by the method for electrochemical deposition, carrier material is as cathode, metal
Lithium is as anode, in 0.1-4mA/cm2Current density under, in deposited on supports 8-10mAh/cm2Metal simple-substance.
2. a kind of metal secondary batteries, it is characterised in that made using metal secondary batteries composite negative pole material described in claim 1
For battery cathode.
3. metal secondary batteries composite negative pole material described in claim 1 is avoiding the purposes in Li dendrite.
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| CN109873122B (en) * | 2017-12-04 | 2021-08-03 | 北京壹金新能源科技有限公司 | Ultrathin metal lithium complex and preparation method and application thereof |
| CN108933258A (en) * | 2018-06-27 | 2018-12-04 | 淄博火炬能源有限责任公司 | The preparation method of the all-solid lithium-ion battery of three-dimensional composition metal cathode of lithium |
| CN110752346B (en) * | 2018-07-23 | 2021-02-12 | 北京好风光储能技术有限公司 | Back-to-back deposition type metal cathode and back-to-back deposition type metal cathode battery |
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| CN104752682A (en) * | 2015-03-16 | 2015-07-01 | 山东玉皇新能源科技有限公司 | Preparation method of sulphur/carbon composite cathode material for lithium sulphur battery |
| CN105514438A (en) * | 2015-12-25 | 2016-04-20 | 清华大学深圳研究生院 | Sodium-ion battery electrode material, electrode and battery |
| CN105789559A (en) * | 2016-04-21 | 2016-07-20 | 清华大学 | Flexible lithium metal cell negative pole and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104752682A (en) * | 2015-03-16 | 2015-07-01 | 山东玉皇新能源科技有限公司 | Preparation method of sulphur/carbon composite cathode material for lithium sulphur battery |
| CN105514438A (en) * | 2015-12-25 | 2016-04-20 | 清华大学深圳研究生院 | Sodium-ion battery electrode material, electrode and battery |
| CN105789559A (en) * | 2016-04-21 | 2016-07-20 | 清华大学 | Flexible lithium metal cell negative pole and preparation method thereof |
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