CN208352138U - A kind of electrochemical energy storage device - Google Patents
A kind of electrochemical energy storage device Download PDFInfo
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- CN208352138U CN208352138U CN201721834095.2U CN201721834095U CN208352138U CN 208352138 U CN208352138 U CN 208352138U CN 201721834095 U CN201721834095 U CN 201721834095U CN 208352138 U CN208352138 U CN 208352138U
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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
- Y02E60/13—Energy storage using capacitors
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Abstract
The utility model relates to a kind of electrochemical energy storage devices, including the anode conducting plate being sequentially distributed, the anode being supported on anode conducting plate, porous septum, the cathode being supported on cathode conductive plate and cathode conductive plate, electrolyte is filled between the anode and cathode, the first painting layer of charcoal is added between the anode conducting plate and anode, the second painting layer of charcoal is added between the cathode conductive plate and cathode, the anode includes the first conducting carbonaceous material and lithium metal material；The cathode includes the second conducting carbonaceous material and lithium-containing compound material.Compared with prior art, the utility model has energy density more higher than supercapacitor under low-power requirements；Under high power requirements, there is power density more higher than lithium ion battery, and there is good power characteristic.
Description
Technical field
The utility model relates to technical field of chemical power, and in particular to a kind of electrochemical energy storage device.
Background technique
Auto industry is made that significant contribution to world economy and human society, and automobile is considered to be modern society's freedom
With the symbol of liberation.It however as the continuous expansion of automobile industry, needs to consume a large amount of fossil fuel, and environment is generated
Very big influence.Be more than in world wide according to statistics 50% petroleum for transporting, the pollutant of more than half is from vehicle tail
Gas.It flourishing bring energy and environmental problem for automobile industry, electric car is very effective solution, and
Different electric cars many in recent years have been incorporated into market.
However, even state-of-the-art electric car is also faced with three main problems: limited stroke mileage, it is slower
Priming speed and expensive price.These problems are related to the electrical source of power of vehicle.Most widely used electrical source of power includes lithium
Ion battery, fuel cell and electrochemical capacitor.Lithium ion battery passes through electrochemical reaction storage energy, electrochemical capacitor
It is that electric double layer is formed by the interface between electrolyte and electronic conductor to store electric energy.
The advantages of each energy storage system has oneself and disadvantage.Due to electrochemical capacitor and lithium ion battery they
High power density or high-energy density can be provided respectively, therefore are considered as most potential energy storage system.Lithium ion
Lithium ion from cathode deintercalation moves to anode to battery during discharge, and it is 120- that the process, which can provide high chemical energy,
250Wh/kg.However, since lithium ion is mobile low with the insertion speed of deintercalation, thus power density is at a fairly low, only 200W/kg
Left and right.In electrochemical capacitor, the main source of energy is the adsorption/desorption process of electrolyte on the electrode, the process with
The chemical reaction process of lithium ion battery is compared and is exceedingly fast.Therefore, electrochemical capacitor power density can achieve 2-10kW/kg very
To higher.But since ionic adsorption/desorption occurs over just electrode active material performance, device integral energy density is lower,
Only 5~8Wh/kg.
In order to solve these problems, researcher proposes different solutions.Most widely used solution is
Develop the hybrid system being made of electrochemical capacitor electrode and battery electrode.In this configuration, anode by anion can
Inverse non-faraday reaction storage charge, while cathode realizes lithium ion insertion/deintercalation using reversible faraday's reaction.With tradition
Electrochemical capacitor is compared, and hybrid super capacitor shows higher energy density.Telcordia has been developed for one
The new equipment of entitled non-aqueous asymmetric hybrid electrochemical supercapacitor is planted, wherein Li4Ti5O12As negative electrode material, activity
Charcoal is as positive electrode.However, the energy density of these devices is too low, the energy storage system of electric car cannot function as.
Previous existing document discloses can be by adding the hard of stable lithium metal material powder (SLMP) layer on the surface
Carbon (HC) cathode replaces lithium-ion capacitor [W.J.Cao and J.P.Zheng, the J. Power of conventional activated carbon cathode
Sources,213,180(2012).].The lithium bisque of addition can increase the open-circuit voltage of capacitor, and ensure the electricity in charging
Less ion is consumed in solution liquid.The lithium-ion capacitor can store about 5 times of energy more much than Conventional electrochemical capacitor
It measures (< 25Wh/Kg), and there is high power density.Nevertheless, but energy density still do not reach the need of practical application
It wants, is analyzed by energy storage mechnism it is found that the cell performance cathode based on active carbon and pre- embedding lithium is difficult to further increase lithium-ion capacitance
The energy density of device, therefore, it is necessary to do more work in terms of the structure of power supply apparatus.
Utility model content
The purpose of this utility model is exactly to provide a kind of while having to overcome the problems of the above-mentioned prior art
High power density and high-energy density and can effective hoisting power characteristic electrochemical energy storage device.
The purpose of this utility model can be achieved through the following technical solutions: a kind of electrochemical energy storage device, should
Storage device includes the anode conducting plate being sequentially distributed, the anode being supported on anode conducting plate, porous septum, is supported on cathode
Cathode and cathode conductive plate on conductive plate fill electrolyte solution, the anode conducting plate between the anode and cathode
The first painting layer of charcoal is added between anode, and the second painting layer of charcoal, the anode packet are added between the cathode conductive plate and cathode
The first conducting carbonaceous material and lithium metal material are included, the cathode includes the second conducting carbonaceous material and lithium-containing compound material
Material.
The structure anode of apparatus of the present invention be containing the first conducting carbonaceous material and lithium metal material, can maintain compared with
Low work potential and the balance of electrolyte ion is provided, to provide higher energy density.Cathode is lithium-containing compound
The combination of material and the second conducting carbonaceous material, positive and negative interpolar have porous septum that anode and cathode is avoided directly to contact, and electrolyte is abundant
Fill the pore structure of positive and negative pole material.This new type lithium ion capacitor is able to achieve the balance of energy density and power density, and
And process for producing is simple, performance has controllability.Due to using this unique structure, so that in low-power output,
The device will reflect the characteristic of lithium ion battery and provide high-energy density.In high-power output, which will show excess of export
The feature of grade capacitor simultaneously provides high power density.Therefore, this mixed type lithium ion capacitor may be implemented to realize height simultaneously
Power density and high-energy density.In addition, due to dividing between anode conducting plate and anode, between cathode conductive plate and cathode
The first painting layer of charcoal and second is not added and applies layer of charcoal, can not only be increased the peel strength of cathode and anode, be reduced cathode and anode
The usage amount of middle binder, simultaneously, additionally it is possible to reduce the contact resistance of cathode and anode, the power for promoting device significantly is special
Property.
The material of the painting layer of charcoal be electrically conductive graphite or carbon black, it is described apply layer of charcoal with a thickness of 1~5 μm.
The mass ratio of first conducting carbonaceous material and lithium metal material is (3~30): 1, first conductive carbonaceous
Material is mixed selected from one or more of hard carbon, soft carbon, graphitic carbon, carbon nanotube, carbon nano-fiber.
In the anode, the lithium metal material is evenly mixed in inside the first conducting carbonaceous material；
Alternatively, the lithium metal material and the first conducting carbonaceous material are plate, and it is disposed in parallel in the first painting layer of charcoal
Between porous septum.
The mass ratio of second conducting carbonaceous material and lithium-containing compound material is (0.05~5): 1, and described second
The mass ratio of conducting carbonaceous material and lithium metal material is 1:(0.001~0.1), the porosity of second conducting carbonaceous material
Greater than the porosity of the first conducting carbonaceous material.
Second conducting carbonaceous material is selected from active carbon, carbon nanotube, Activated Carbon Nanotubes and activated carbon Nanowire
The mixing of one or more of group of composition is tieed up, the lithium-containing compound material, which is selected from, contains lithium metal oxide or lithium salts, tool
Body such as LiMn2O4、LiV3O8、LiFePO4、xLi2MnO3·(1-x)LiMO2One or more of mixing；Described second is conductive
The conductivity of carbonaceous material is greater than 1S/cm, and the specific surface area of the second conducting carbonaceous material is greater than 500m2/ g, the second conductive carbonaceous
The specific capacitance of material is greater than 50F/g, and the porosity of the second conducting carbonaceous material is greater than 50%.
In the cathode, lithium-containing compound material is evenly mixed in inside the second conducting carbonaceous material；
Alternatively, the lithium-containing compound material and the second conducting carbonaceous material are plate, and it is disposed in parallel in the second painting
Between layer of charcoal and porous septum.
The material of the anode conducting plate and cathode conductive plate is copper foil or aluminium foil.
The electrolyte solution is lithium salt solution, and preferably LiPF6 is electrolyte, with ethylene carbonate, diethyl carbonate
Mixed solution with dimethyl carbonate is the electrolyte of solvent.
Compared with prior art, the beneficial effects of the utility model are embodied in following several respects:
(1) electrochemical energy storing device of the invention, the characteristic with lithium ion battery and supercapacitor are defeated in low current
Out, under the operating condition of low-power, which has the attribute similar to lithium ion battery, has higher energy density；In high current
Under output, high-power operating condition, which has the characteristic similar to supercapacitor, has high power density；
(2) electrochemical energy storing device of the invention has energy density more higher than supercapacitor, and has than lithium
The higher power density of ion battery electrode, the high power of the high-energy density and supercapacitor that combine lithium ion battery are close
The advantages of spending can satisfy the demand of the demand of high-energy density and the high power density of energy storage system.
(3) load applies layer of charcoal on cathode and anode conducting plate, can not only increase the peel strength of cathode and anode, subtract
The usage amount of binder in few cathode and anode, simultaneously, additionally it is possible to reduce the contact resistance of cathode and anode, significant ground lifter
The power characteristic of part.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the utility model；
Fig. 2 is 2 structural schematic diagram of the embodiments of the present invention；
Fig. 3 is 3 structural schematic diagram of the embodiments of the present invention；
Fig. 4 is comparative example 1, the charging and discharging curve of comparative example 2 and embodiment 3 at low currents；
Fig. 5 is comparative example 1, the charging and discharging curve of comparative example 2 and embodiment 3 under high currents；
Fig. 6 is that the Ragone of comparative example 1, comparative example 2 and embodiment 3 schemes；
Fig. 7 is embodiment 4 in 60C high magnification capacity retention ratio and coulombic efficiency figure；
Fig. 8 is 3 high rate performance comparison diagram of embodiment 5 and comparative example.
Wherein, 1 is anode conducting plate, and 2 apply layer of charcoal for first, and 3 be anode, and 31 be the first conducting carbonaceous material, and 32 be lithium
Metal material, 4 be porous septum, and 5 be cathode, and 51 be the second conducting carbonaceous material, and 52 be lithium-containing compound material, and 6 be second
Layer of charcoal is applied, 7 be cathode conductive plate.
Specific embodiment
It elaborates below to the embodiments of the present invention, the present embodiment before being with technical solutions of the utility model
It puts and is implemented, the detailed implementation method and specific operation process are given, but the protection scope of the utility model is unlimited
In following embodiments.
Embodiment 1
A kind of electrochemical energy storage device, single-cell structure is as shown in Figure 1, the device includes the anode being sequentially distributed
Conductive plate 1, the carbon black first being supported on anode conducting plate 1 apply layer of charcoal 2, are supported on the anode 3 that carbon black first applies layer of charcoal 2, more
Hole diaphragm 4, cathode 5, the carbon black second being supported on cathode conductive plate 7 apply layer of charcoal 6 and cathode conductive plate 7, wherein anode
Conductive plate 1 is copper foil, and cathode conductive plate 7 is aluminium foil.Wherein, electrolyte LiPF6 (EC:DMC=is filled between cathode 5 and anode 3
1:1wt%), anode 3 includes the first conducting carbonaceous material 31 and lithium metal material 32, wherein the first conducting carbonaceous material 31 is stone
Ink, lithium metal material are lithium metal powder SLMP, and the two uniformly mixes；Cathode active material layer 5 includes the second conductive carbonaceous material
Material 51 and lithium-containing compound material 52, the second conducting carbonaceous material 51 are active carbon, and lithium-containing compound material 52 is ferric phosphate
Lithium, the two uniformly mix.
Embodiment 2
A kind of electrochemical energy storage device, single-cell structure are as shown in Figure 2.The device includes the anode being sequentially distributed
Conductive plate 1, the electrically conductive graphite first being supported on anode conducting plate 1 apply layer of charcoal 2, are supported on electrically conductive graphite first and apply layer of charcoal 2
Anode 3, porous septum 4, cathode 5, the electrically conductive graphite second being supported on cathode conductive plate 7 apply layer of charcoal 6 and cathode conductive plate
7, wherein anode conducting plate 1 is copper foil, and cathode conductive plate 7 is aluminium foil.Wherein, electrolyte is filled between cathode 5 and anode 3
LiPF6 (EC:DMC:DEC=1:1:1wt%), anode 3 include the first conducting carbonaceous material 31 and lithium metal material 32, and first leads
Electric carbonaceous material 31 is graphite, and lithium metal material is lithium metal powder SLMP, and the two is sequentially placed according to sequence as shown in the figure；Yin
Pole active material layer 5 includes the second conducting carbonaceous material 51 and lithium-containing compound material 52, and the second conducting carbonaceous material 51 is to live
Property charcoal, lithium-containing compound material 52 is LiMn2O4, and the two uniformly mixes, and the two uniformly mixes.
Embodiment 3
A kind of electrochemical energy storage device, single-cell structure are as shown in Figure 3.The device includes the anode being sequentially distributed
Conductive plate 1, the electrically conductive graphite first being supported on anode conducting plate 1 apply layer of charcoal 2, are supported on electrically conductive graphite first and apply layer of charcoal 2
Anode 3, porous septum 4, cathode 5, the electrically conductive graphite second being supported on cathode conductive plate 7 apply layer of charcoal 6 and cathode conductive plate
7, wherein anode conducting plate 1 is copper foil, and cathode conductive plate 7 is aluminium foil.Wherein, electrolyte is filled between cathode 5 and anode 3
LiPF6 (EC:DMC=1:1wt%), anode 3 include the first conducting carbonaceous material 31 and lithium metal material 32, and the first conduction contains
Carbon material 31 is hard carbon, and lithium metal material 32 is lithium metal thin slice 32, and the two is sequentially placed according to sequence as shown in the figure, thin lithium piece
It is covered in hard carbon layer outer surface；Cathode active material layer 5 includes the second conducting carbonaceous material 51 and lithium-containing compound material 52, yin
Pole active material layer 5 includes the second conducting carbonaceous material 51 and lithium-containing compound material 52, and the second conducting carbonaceous material 51 is to live
Property charcoal, lithium-containing compound material 52 is LiMn2O4, and the two uniformly mixes, and the two uniformly mixes.
In the present embodiment, the mass ratio of lithium-containing compound LiMn2O4 and the second carbonaceous material active carbon is 3 in cathode:
7, it is 1 μm that electrically conductive graphite, which applies carbon layer,.
Comparative example 1
According to anode electrode structure described in embodiment 3, it is prepared for corresponding anode electrode, electrically conductive graphite coating layer thickness is
1μm.Meanwhile as a control group, according to cathode electrode structure described in embodiment 3, corresponding cathode electrode is prepared, it is different
It is that the second carbonaceous material, only lithium-containing compound material lithium manganate are not contained in cathode.According to monocell described in embodiment 3
Structure assembles them into button-shaped full battery Q2.
Comparative example 2
According to anode electrode structure described in embodiment 3, it is prepared for corresponding anode electrode, electrically conductive graphite coating layer thickness is
1μm.Meanwhile as a control group, according to cathode electrode structure described in embodiment 3, corresponding cathode electrode is prepared, it is different
It is that lithium-containing compound material, only the second carbonaceous material active carbon are not contained in cathode.According to monocell described in embodiment 3
Structure assembles them into button-shaped full battery Q3.
The charge-discharge test under same current density is carried out to full battery prepared by embodiment 3 and comparative example 1, comparative example 2.
Fig. 4 is the charging/discharging voltage curve of three devices under low current；Fig. 5 is under high current, and the charging/discharging voltage of three devices is bent
Line；Fig. 6 is the Ragone figure (being based on active material) of three devices.
Analysis chart 4, Fig. 5 and Fig. 6, it can be deduced that, under low current density, the capacity of device will obviously be lower than embodiment 3
Comparative example 1 (battery), but it is better than comparative example 2 (capacitor)；Equally, at higher current densities, the capacity of 3 device of embodiment is obvious
Higher than comparative example 1 (battery), but it is lower than comparative example 2 (capacitor).It means that under low current density, structure described in embodiment 3
Device energy density it is higher than comparative example 2 (capacitor), and power density is higher than comparative example 1 (battery)；It is close in high current
Under degree, the device energy density of structure described in embodiment 3 is higher than comparative example 1 (battery), and power density and comparative example 2
(capacitor) is suitable.As can be seen that embodiment 3 can alleviate energy density and saturation effect between battery and capacitor well
Lack of uniformity.
Embodiment 4
According to cathode described in embodiment 1 and anode electrode structure, corresponding anode and cathode electrode is prepared, wherein cathode
The mass ratio of middle lithium-containing compound LiFePO4 and the second carbonaceous material active carbon is 2:8, and carbon black conductive coating layer thickness is 2 μm.
Button-shaped full battery Q4 is assembled them into according to the single-cell structure that embodiment 1 is stated.By button-shaped full battery Q4 in 60C high magnification
Lower test, test results are shown in figure 7.It under 60C high magnification, is recycled by 5000 times, the capacity retention ratio of device is still super
Cross 80%, cycle efficieny is close to 100%.
Embodiment 5
According to cathode as described in example 2 and anode electrode structure, corresponding anode and cathode electrode, electrically conductive graphite are prepared
Coating layer thickness is 2 μm.Button-shaped full battery Q5 is assembled them into according to single-cell structure as described in example 2.
Comparative example 3
Using identical electrode material in embodiment 5, anode electrode and cathode electrode are prepared, not with electrode in embodiment 5
It is with place, cathode conductive plate and the uncoated electrically conductive graphite of anode conducting plate in comparative example 3.According to described in embodiment 2
Single-cell structure by cathode and anode assembling at button-shaped full battery Q6.
The test of high rate performance under the same terms is carried out to two kinds of devices of embodiment 7 and comparative example 3, test result is as schemed
Shown in 8.As can be seen that the high rate performance of 3 device of comparative example is more far short of what is expected than 5 device of embodiment under same test condition,
Difference becomes apparent under high magnification.Therefore, the multiplying power property of device can effectively be promoted by electrically conductive graphite being coated on conductive plate, be mentioned
The capacity retention ratio of high device.
Claims (5)
1. a kind of electrochemical energy storage device, which is characterized in that the storage device includes the anode conducting plate being sequentially distributed, bears
Anode, porous septum, the cathode being supported on cathode conductive plate and the cathode conductive plate being loaded on anode conducting plate, the sun
Electrolyte solution is filled between pole and cathode, the first painting layer of charcoal is added between the anode conducting plate and anode, and the cathode is led
The second painting layer of charcoal is added between battery plate and cathode, the anode includes the first conducting carbonaceous material and lithium metal material；It is described
Cathode include the second conducting carbonaceous material and lithium-containing compound material；
The mass ratio of first conducting carbonaceous material and lithium metal material is (3~30): 1, first conducting carbonaceous material
It is mixed selected from one or more of hard carbon, soft carbon, graphitic carbon, carbon nanotube, carbon nano-fiber；
In the anode, the lithium metal material is evenly mixed in inside the first conducting carbonaceous material；Alternatively, the lithium metal
Material and the first conducting carbonaceous material are plate, and are disposed in parallel between the first painting layer of charcoal and porous septum；
The mass ratio of second conducting carbonaceous material and lithium-containing compound material is (0.05~5): 1, and described second is conductive
The mass ratio of carbonaceous material and lithium metal material is 1:(0.001~0.1), the porosity of second conducting carbonaceous material is greater than
The porosity of first conducting carbonaceous material；
In the cathode, lithium-containing compound material is evenly mixed in inside the second conducting carbonaceous material；Alternatively, described contain lithiumation
It closes object material and the second conducting carbonaceous material is plate, and be disposed in parallel between the second painting layer of charcoal and porous septum.
2. a kind of electrochemical energy storage device according to claim 1, which is characterized in that described first apply layer of charcoal and
Second apply layer of charcoal material be electrically conductive graphite or carbon black, it is described apply layer of charcoal with a thickness of 1~5 μm.
3. a kind of electrochemical energy storage device according to claim 1, which is characterized in that second conductive carbonaceous
Material is selected from one or more of group of active carbon, carbon nanotube, Activated Carbon Nanotubes and active carbon nano-fiber composition
Mixing, the lithium-containing compound material, which is selected from, contains lithium metal oxide or lithium salts, the conductivity of second conducting carbonaceous material
Greater than 1S/cm, the specific surface area of the second conducting carbonaceous material is greater than 500m2The specific capacitance of/g, the second conducting carbonaceous material are greater than
The porosity of 50F/g, the second conducting carbonaceous material are greater than 50%.
4. a kind of electrochemical energy storage device according to claim 1, which is characterized in that the anode conducting plate with
And the material of cathode conductive plate is copper foil or aluminium foil.
5. a kind of electrochemical energy storage device according to claim 1, which is characterized in that the electrolyte solution is
Lithium salt solution.
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| CN201721834095.2U CN208352138U (en) | 2017-12-25 | 2017-12-25 | A kind of electrochemical energy storage device |
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| CN201721834095.2U CN208352138U (en) | 2017-12-25 | 2017-12-25 | A kind of electrochemical energy storage device |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109974907A (en) * | 2019-03-15 | 2019-07-05 | 钛深科技(深圳)有限公司 | Integrated pliable pressure sensor of actively powering |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109974907A (en) * | 2019-03-15 | 2019-07-05 | 钛深科技(深圳)有限公司 | Integrated pliable pressure sensor of actively powering |
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