CN105633418B - A kind of lithium sky cell cathode Pt/UIO-66 composite materials and its preparation method - Google Patents
A kind of lithium sky cell cathode Pt/UIO-66 composite materials and its preparation method Download PDFInfo
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to technical field of material chemistry, a kind of 66 composite materials of lithium sky cell cathode Pt/UIO and its preparation method are disclosed.The method is：(1) synthesis of 66 metal-organic framework materials of UIO：(2) preparation of 66 composite materials of Pt/UIO：The solution of 66 metal-organic framework materials of UIO and platiniferous element is subjected to ultrasonic disperse, centrifuges, dries, grinding is passed through reducibility gas and is restored using temperature programming, obtains 66 composite materials of Pt/UIO.Pt is carried on by the present invention to be held with bigger serface, macropore in the metal-organic framework materials UIO 66 of microcellular structure, it can effectively improve the adhesive force of Pt components and carrier, straight-through duct is conducive to the transmission of oxygen and active oxygen, to improve the specific capacity and cycle performance of battery；The preparation method of the present invention is simple to operation, is suitble to large-scale industrial production.
Description
Technical field
The invention belongs to technical field of material chemistry, are related to a kind of composite material, and in particular to one kind is with metal organic framework material
Material is the Pt/UIO-66 composite material and preparation methods of the lithium sky cell cathode of carrier.
Background technology
With the continuous development of human society, lack of energy, environmental pollution getting worse find novel non-polluting energy sources
It has been to be concerned by more and more people.Lithium sky battery be one kind using lithium metal as cathode, air (oxygen) be used as cathode active material,
A kind of lithium secondary battery that chemical energy and electric energy mutually convert is realized by the chemical reaction between oxygen and lithium.With lithium ion two
Primary cell is compared, and lithium sky battery has high theoretical capacity, with the Mass Calculation of cathode lithium, up to 11140Wh/kg, with stone
Oil phase is worked as.Therefore lithium sky battery be considered as it is a kind of have high-energy density, it is environmental-friendly, it is easy miniaturization and cheap and easy to get two
Primary cell is also considered as the following power battery first choice, great scale application value and foreground.
However, being limited to the influence of cathodic oxygen reduction and oxygen evolution reaction efficiency, there are still poor circulation, mistakes for lithium sky battery
The shortcomings of voltage is big and high rate performance is poor becomes the maximum bottleneck for hindering lithium sky battery practical application.And battery is cloudy among these
Pole plays a part of can not ignore.Therefore a kind of suitable cathode material is developed, charge and discharge overvoltage can be reduced, improve charge and discharge
Electrical efficiency and invertibity, this has profound significance for the development of lithium sky battery and scale application.
Currently, people mostly use Carbon Materials (activated carbon, carbon nanotube, graphene etc.) carried noble metal or base metal is made
For lithium sky battery cathode material.Novel cathode material must be developed in order to seek higher performance.MOFs materials are as porous material
Emerging member, there is pore structure and surface property is adjustable, high-specific surface area and Kong Rong, uniform pore-size distribution and insatiable hunger
With the peculiar properties such as metallic site, therefore, MOFs materials are expected to the completely new lithium sky battery cathode material as function admirable.
Invention content
It is an object of the invention to be directed to existing lithium sky battery cathode material catalytic activity not enough and poor circulation etc. is scarce
It falls into, a kind of Pt/UIO-66 composite materials of lithium sky cell cathode is provided.Precious metals pt is dispersed in micropore gold by the present invention
Belong in organic backbone UIO-66 crystal, the Pt/UIO-66 for having prepared the specific capacity and cycle performance that can improve battery is multiple
Condensation material.
Another object of the present invention is to provide the preparation sides of the Pt/UIO-66 composite materials of above-mentioned lithium sky cell cathode
Method.
The purpose of the present invention is achieved through the following technical solutions：
A kind of lithium sky cell cathode Pt/UIO-66 composite materials, be using UIO-66 metal-organic framework materials as carrier,
Pt uniform loads are obtained in UIO-66 metal-organic framework materials.
The lithium sky cell cathode preparation method of Pt/UIO-66 composite materials, specifically includes following steps：
(1) synthesis of UIO-66 metal-organic framework materials：
(2) preparation of Pt/UIO-66 composite materials：
The solution of UIO-66 metal-organic framework materials and platiniferous element is subjected to ultrasonic disperse, centrifuges, dries, grinding,
It is passed through reducibility gas and is restored using temperature programming, obtain Pt/UIO-66 composite materials.
The weight ratio of Pt and UIO-66 metal-organic framework materials is in the solution of step (2) the platiniferous element：(1-
10)：100；The mass volume ratio of step (2) the UIO-66 metal-organic framework materials and the solution of platiniferous element is (0.05-
0.1)g：(5-15)ml.
The solution of step (2) the platiniferous element is platinum acid chloride solution.
Step (2) described program heats up：
(a) temperature-rise period：With the speed of 0.3-1.0 DEG C/min 150-250 DEG C is risen to from room temperature；
(b) thermostatic process：1-3h is kept in 150-250 DEG C；
(c) temperature-fall period：Temperature fall.
The time of step (2) described ultrasonic disperse is 10-30min, and step (2) described centrifugal rotational speed is 7000-9000r/
Min, centrifugation time 10-20min；The gas used that restores is hydrogen.
Step (2) the ultrasonic power 200-300W；Frequency 40KHZ.The temperature of step (2) described drying is 100-140
℃；Drying time 12-24h.
The specific method of the synthesis of step (1) the UIO-66 metal-organic framework materials be by ZrCl4With to benzene two
Formic acid (H2BDC) be dissolved in organic solvent, at room temperature stirring and dissolving, by solution move into hydrothermal reaction kettle in, temperature programming into
Row hydro-thermal reaction, temperature program are：Be heated to 100-150 DEG C from room temperature with 5-10 DEG C/min, and keep the temperature 20-28h, later again with
The rate of temperature fall of 0.4-0.6 DEG C/min is down to room temperature, and UIO-66 metal-organic framework materials are made in subsequent processing.
The ZrCl4：Terephthalic acid (TPA)：Organic solvent is (0.25-0.35) g：(0.15-0.25)g：(40-60)mL；Institute
It is dimethylformamide (DMF) to state organic solvent；The mixing time is 10-30min.
The subsequent processing refers to filtering hydro-thermal reaction product with DMF, and chloroform impregnates, and centrifugation is done at 100-140 DEG C
Dry 12-24h.The soaking time is 12-48h.
UIO-66 mainly passes through Zr4+A kind of metal organic framework for being coordinated and being formed with terephthalic acid (TPA) has higher
Specific surface area and Kong Rong, aperture be aboutAnd with good hydrothermal stability and chemical stability and mechanicalness
Can, on the one hand smaller aperture is conducive to the fixation of Pt catalyst and the control of size, be on the other hand conducive to oxygen
Absorption, straight-through duct is conducive to the migration of oxygen and active oxygen, while its good stability contributes to it to exist as cathode material
It makes and use keeps original skeleton structure in the process.Therefore, the material that prepared by the present invention can improve charge/discharge capacity and
Cycle performance.
Compared with prior art, the present invention having the advantages that：
(1) active component Pt is carried on the organic bone of metal for holding microcellular structure with bigger serface, macropore by the present invention
In frame material UIO-66, the adhesive force of Pt components and carrier is can effectively improve, straight-through duct is conducive to oxygen and active oxygen
Transmission, to improve the specific capacity and cycle performance of battery；
(2) Pt is carried on UIO-66 porous materials by infusion process by forms Pt/UIO-66 composite materials by the present invention, energy
Pt is set equably to be spread in the skeleton of UIO-66 with nanometer small particles form；
(3) preparation method of the invention is simple to operation, is suitble to large-scale industrial production.
Description of the drawings
Fig. 1 is Pt/UIO-66 composite material and UIO-66 metal-organic framework materials (UIO-66) prepared by embodiment 2
XRD diffraction patterns；Pt/UIO-66 in figure is Pt/UIO-66 composite materials；
Fig. 2 is Pt/UIO-66 composite materials (Fig. 2 a) prepared by embodiment 2 and UIO-66 metal-organic framework materials (figure
SEM figures 2b)；
Fig. 3 is Pt/UIO-66 composite material and UIO-66 metal-organic framework materials (UIO-66) prepared by embodiment 2
N2Absorption/desorption isotherm (Fig. 3 a) and graph of pore diameter distribution (Fig. 3 b)；Pt/UIO-66 in figure is Pt/UIO-66 composite materials；
Fig. 4 is the TEM figures of Pt/UIO-66 composite materials prepared by embodiment 2；
Fig. 5 is that Pt/UIO-66 composite materials prepared by Examples 1 and 2 and absorbent charcoal material (AC) are used for cathode material
Complete discharge curve (current density 100mA/g)；
Fig. 6 is the cycle performance figure (current density that Pt/UIO-66 composite materials prepared by embodiment 2 are used for cathode material
100mA/g limits capacity 2000mAh/g).
Specific implementation mode
With reference to implementation, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
(1) by the ZrCl of 0.26g4With the terephthalic acid (TPA) H of 0.18g2BDC is dissolved in 40mL dimethylformamides (DMF)
In, it stirs in 10min, is fully moved into solution in the ptfe autoclave of 100mL after dissolving, then by reaction kettle at room temperature
It is placed in stainless steel outer sleeve and seals；Retort is put into temperature programming baking oven and carries out hydro-thermal reaction, temperature program is：With 5
DEG C/min is heated to 100 DEG C from room temperature, and keeps 28h, solution is down to by room temperature with the rate of temperature fall of 0.4 DEG C/min again later；
After solution is cooled to room temperature, crystal is filtered with DMF, chloroform immersion centrifuges afterwards for 24 hours, and 12h is dried in vacuo at 100 DEG C, makes
Obtain UIO-66 metal-organic framework materials (i.e. UIO-66)；
(2) UIO-66 and 5ml the chloroplatinic acid (H of 0.05g is weighed2PtCl6·6H2O, 1mg/ml), it is placed in Ultrasound Instrument and carries out
Ultrasonic 10min (ultrasonic power 200W；Frequency 40KHZ), it is then centrifuged for, rotating speed 7000r/min, centrifuges 20min；It is placed in again
Vacuum drying 12h at 100 DEG C, grinding, the powder after grinding is put into tube furnace, is passed through hydrogen and with the speed of 0.3 DEG C/min
Degree rises to 150 DEG C from room temperature, and constant temperature 3h carries out hydrogen reducing, and Temperature fall obtains Pt/UIO-66 composite materials.
Embodiment 2
(1) by the ZrCl of 0.2820g4With the terephthalic acid (TPA) H of 0.2030g2BDC is dissolved in 50mL dimethylformamides
(DMF) it in, stirs in 20min, is fully moved into solution in the ptfe autoclave of 100mL after dissolving at room temperature, then will
Reaction kettle is placed in stainless steel outer sleeve and seals；Retort is put into temperature programming baking oven and carries out hydro-thermal reaction, temperature program
For：125 DEG C are heated to from room temperature with 7.5 DEG C/min, and keeps for 24 hours, later again dropping solution with the rate of temperature fall of 0.5 DEG C/min
To room temperature；After solution is cooled to room temperature, crystal is filtered with DMF, chloroform centrifuges after impregnating 36h, is dried in vacuo at 120 DEG C
UIO-66 metal-organic framework materials (i.e. UIO-66) are made in 18h；
(2) UIO-66 and 10ml the chloroplatinic acid (H of 0.075g is weighed2PtCl6·6H2O, 1mg/ml), be placed in Ultrasound Instrument into
Row ultrasound 20min (ultrasonic power 250W；Frequency 40KHZ), it is then centrifuged for, rotating speed 8000r/min, centrifuges 15min；It is placed in again
Vacuum drying 18h, then grinds at 120 DEG C, and the powder after grinding is put into tube furnace, is passed through hydrogen and with 0.6 DEG C/min
Speed rise to 200 DEG C from room temperature, constant temperature 2h carries out hydrogen reducing, and Temperature fall obtains Pt/UIO-66 composite materials.
Embodiment 3
(1) by the ZrCl of 0.32g4With the terephthalic acid (TPA) H of 0.22g2BDC is dissolved in 60mL dimethylformamides (DMF)
In, it stirs in 30min, is fully moved into solution in the ptfe autoclave of 100mL after dissolving, then by reaction kettle at room temperature
It is placed in stainless steel outer sleeve and seals；Retort is put into temperature programming baking oven and carries out hydro-thermal reaction, temperature program is：With 10
DEG C/min is heated to 150 DEG C from room temperature, and keeps 20h, solution is down to by room temperature with the rate of temperature fall of 0.6 DEG C/min again later；
After solution is cooled to room temperature, crystal is filtered with DMF, chloroform centrifuges after impregnating 48h, is dried in vacuo at 140 DEG C for 24 hours, system
Obtain UIO-66 metal-organic framework materials (i.e. UIO-66)；
(2) UIO-66 and 15ml the chloroplatinic acid (H of 0.1g is weighed2PtCl6·6H2O, 1mg/ml), it is placed in Ultrasound Instrument and carries out
Ultrasonic 30min (ultrasonic power 300W；Frequency 40KHZ), it is then centrifuged for, rotating speed 9000r/min, centrifuges 10min；It is placed in 140
Vacuum drying for 24 hours, is then ground at DEG C, and obtained powder is put into tube furnace, is passed through hydrogen, and with the speed of 1.0 DEG C/min
Degree rises to 250 DEG C from room temperature, and constant temperature 1h carries out hydrogen reducing, and Temperature fall obtains Pt/UIO-66 composite materials.
Structural characterization and performance test：
(1) the XRD diffraction patterns for the Pt/UIO-66 composite materials and UIO-66 that prepared by embodiment 2
XRD tests carry out on German Bruker companies D8 ADVANCE type diffractometers.Use copper target Ka light sources (λ
=0.15432nm), graphite monochromator, tube voltage 40kV, tube voltage 40mA.Step-length is 0.02 ° in 5~60 ° of sections,
Sweep speed is 17.7 seconds/step.Test results are shown in figure 1.
Fig. 1 is Pt/UIO-66 composite materials prepared by embodiment 2 and the X-ray powder diffraction spectrogram of UIO-66.From figure
UIO-66 samples be can be seen that after carried noble metal Pt, compared with the collection of illustrative plates of pure UIO-66, appearance position consistency, spectrogram
Any variation does not occur, shows that Pt/UIO-66 maintains the crystal structure of original material.Pure Pt angle be 39.8,46.2,
64, there is characteristic peak at 81.2, but there is no the diffraction maximum of apparent Pt in figure, illustrate the particle very little of Pt, be uniformly dispersed, do not have
There is the phenomenon that reunion.
(2) SEM photograph for the Pt/UIO-66 composite materials and UIO-66 that prepared by embodiment 2
Situations such as being used for observing sample surface morphology and granular size using FEI XL-30 scanning electron microscope.Test
Condition：Metal spraying, accelerating potential 10kV.Test results are shown in figure 2.Fig. 2 (a) is that the SEM of Pt/UIO-66 composite materials schemes,
The SEM that Fig. 2 (b) is UIO-66 schemes.
Fig. 2 is Pt/UIO-66 composite materials prepared by embodiment 2 and the electron scanning micrograph of UIO-66.From figure
In as can be seen that supporting Pt before and after UIO-66 crystal regular regular hexahedron configuration is all presented, surface topography is consistent, ruler
Very little size shows that the surface topography of crystal during supporting Pt is not affected in 100nm or so.
(3) N for the Pt/UIO-66 composite materials and UIO-66 that prepared by embodiment 22Absorption/desorption isotherm and aperture point
Butut
The UIO-66 using the ASAP-2020 specific surface pore-size distribution instrument of Micro companies of U.S. production prepared by the present invention
The pore structure of metal-organic framework materials and Pt/UIO-66 composite materials is characterized, as a result as shown in Figure 3 and Table 1.Figure
3 (a) is N2Absorption/desorption isotherm, Fig. 3 (b) are graph of pore diameter distribution.
The pore structure parameter of table 1 Pt/UIO-66 composite materials and UIO-66
Table 1 is the hole of Pt/UIO-66 composite materials (Pt/UIO-66) and UIO-66 metal-organic framework materials (UIO-66)
The structural parameters of structure.Fig. 3 is Pt/UIO-66 composite materials (Pt/UIO-66) and UIO-66 metal-organic framework materials (UIO-
66) N2Adsorption-desorption isothermal (Fig. 3 (a)) and graph of pore diameter distribution (Fig. 3 (b)).
Pt/UIO-66 composite materials (Pt/UIO-66) and UIO-66 metal-organic framework materials it can be seen from Fig. 3 (a)
(UIO-66) adsorption isotherm belongs to typical Type-I types thermoisopleth.The BET specific surface area of wherein pure UIO-66 is
835.7m2/ g, Kong Rongwei 0.49cm3/ g, average pore size are(Fig. 3 (b)), the report with documentIt is close.Pt/
The specific surface area of UIO-66 composite materials (Pt/UIO-66) and hole have part decline, are 704.2m2/ g and 0.4cm3/ g, this table
Bright Pt catalyst is supported on the micropore on the surfaces UIO-66, and specific surface area and Kong Rong is caused all to be declined.
(4) the TEM figures of Pt/UIO-66 composite materials prepared by embodiment 2
Fig. 4 is the transmission electron microscope picture of Pt/UIO-66 composite materials prepared by embodiment 2.It can be more clearly from figure
Go out, spherical Pt nano particles are dispersed in UIO-66 crystal (i.e. UIO-66 metal-organic framework materials), and not bright
Aobvious agglomeration.Pt particles substantially 1.3-2.3nm is measured, average 1.8nm, the high degree of dispersion and small size of Pt nano particle particle
Realization to its catalytic performance is highly beneficial.
(5) the Pt/UIO-66 composite materials and absorbent charcoal material that prepared by Examples 1 and 2 are respectively as cathode material
Complete discharge curve (100mA/g)；
Fig. 5 is that Pt/UIO-66 composite materials prepared by Examples 1 and 2 and absorbent charcoal material (AC) are used as cathode material
Continuous charging and discharging curve in the case where current density is 100mA/g.It can be seen from the figure that the active raw material of wood-charcoal relative to no catalyst
For material, Pt/UIO-66 materials greatly facilitate effect to discharge capacity of the cell.The electrode capacity of activated carbon is
2386mAh/g, and the capacity of 3.8wt% (embodiment 1) and the Pt/UIO-66 composite materials of 5wt% (embodiment 2) platinum load capacity
Respectively 6920 and 13315mAh/g, wherein 5wt% Pt/UIO-66 composite materials (embodiment 2) cathodic discharge capacity is current
One of attainable higher capacity of cathode material institute of report and there is one to stablize the higher discharge platform (left sides 2.65V
It is right).By the results show that the Pt/UIO-66 composite properties prepared by the present invention are good, there is higher specific discharge capacity.
(6) cycle performance figure (100mA/g, the limit of Pt/UIO-66 composite materials prepared by embodiment 2 as cathode material
Constant volume 2000mAh/g)；
Fig. 6 is that Pt/UIO-66 composite materials prepared by embodiment 2 as cathode material are 100mA/g in current density, on
Cycle performance figure under limited capacity amount 2000mAh/g.To avoid deep discharge, by the discharge capacity upper limit be set as 2000mAh/g into
Row charge and discharge cycles are tested.It can be seen from the figure that after material recycles eight circles under these conditions, specific discharge capacity is
2000mAh/g or so has higher capacity retention ratio.This explanation, Pt/UIO-66 composite materials play catalysis and make well
With (hydrogen reduction and oxygen evolution reaction), material remains on higher capacity over numerous cycles.
Claims (7)
1. a kind of lithium sky battery cathode material, it is characterised in that：For Pt/UIO-66 composite materials, the Pt/UIO-66 composite woods
Material is to obtain Pt uniform loads in UIO-66 metal-organic framework materials using UIO-66 metal-organic framework materials as carrier
It arrives；
The preparation method of the Pt/UIO-66 composite materials, specifically includes following steps：
(1) synthesis of UIO-66 metal-organic framework materials；
(2) preparation of Pt/UIO-66 composite materials：
The solution of UIO-66 metal-organic framework materials and platiniferous element is subjected to ultrasonic disperse, centrifuges, dries, grinding is passed through
Reducibility gas is simultaneously restored using temperature programming, and Pt/UIO-66 composite materials are obtained；
The weight ratio of Pt and UIO-66 is (1-10) in the solution of step (2) the platiniferous element：100；
Step (2) described program heats up：
(a) temperature-rise period：With the speed of 0.3-1.0 DEG C/min 150-250 DEG C is risen to from room temperature；
(b) thermostatic process：1-3h is kept in 150-250 DEG C；
(c) temperature-fall period：Temperature fall.
2. lithium sky battery cathode material according to claim 1, it is characterised in that：Step (2) the UIO-66 metals are organic
The mass volume ratio of framework material and the solution of platiniferous element is (0.05-0.1) g：(5-15)ml.
3. lithium sky battery cathode material according to claim 1, it is characterised in that：The solution of the platiniferous element is chloroplatinic acid
Solution.
4. lithium sky battery cathode material according to claim 1, it is characterised in that：The time of step (2) described ultrasonic disperse
For 10-30min, step (2) described centrifugal rotational speed is 7000-9000r/min, centrifugation time 10-20min；The reproducibility
Gas is hydrogen.
5. lithium sky battery cathode material according to claim 1, it is characterised in that：Step (2) the ultrasonic power 200-
300W；Frequency 40KHZ；The temperature of step (2) described drying is 100-140 DEG C；Drying time 12-24h.
6. lithium sky battery cathode material according to claim 1, it is characterised in that：Step (1) the UIO-66 metals are organic
The specific method of the synthesis of framework material is by ZrCl4It is dissolved in organic solvent with terephthalic acid (TPA), at room temperature stirring and dissolving,
Solution is moved into hydrothermal reaction kettle, temperature programming carries out hydro-thermal reaction, and temperature program is：It is heated from room temperature with 5-10 DEG C/min
To 100-150 DEG C, and 20-28h is kept the temperature, room temperature, subsequent processing, system are down to the rate of temperature fall of 0.4-0.6 DEG C/min again later
Obtain UIO-66 metal-organic framework materials.
7. lithium sky battery cathode material according to claim 6, it is characterised in that：The ZrCl4：Terephthalic acid (TPA)：It is organic molten
Agent is (0.25-0.35) g：(0.15-0.25)g：(40-60)mL；The organic solvent is dimethylformamide；When the stirring
Between be 10-30min；
The subsequent processing refers to filtering hydro-thermal reaction product with DMF, and chloroform impregnates, and centrifugation is dry at 100-140 DEG C
12-24h。
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| CN108620132A (en) * | 2018-05-03 | 2018-10-09 | 华南理工大学 | A kind of Pt NPs@MOFs photochemical catalysts and the preparation method and application thereof |
| CN109103470A (en) * | 2018-08-30 | 2018-12-28 | 广州大学 | A kind of preparation method of Co/UiO66 catalyst, Co/UiO66 catalyst and its application |
| CN109103464A (en) * | 2018-08-30 | 2018-12-28 | 广州大学 | A kind of preparation method of Catalytic Layer, Catalytic Layer and microbiological fuel cell |
| CN113394368B (en) * | 2020-03-11 | 2023-08-01 | 宁德新能源科技有限公司 | Pole piece and electrochemical device |
| CN113555571B (en) * | 2021-06-28 | 2022-05-17 | 陕西师范大学 | MgPtC0.06H0.32Ti, N-C nano cuboid and preparation method and application thereof |
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