CN107579201B - Multilayer body and preparation method thereof - Google Patents
Multilayer body and preparation method thereof Download PDFInfo
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- CN107579201B CN107579201B CN201710828284.7A CN201710828284A CN107579201B CN 107579201 B CN107579201 B CN 107579201B CN 201710828284 A CN201710828284 A CN 201710828284A CN 107579201 B CN107579201 B CN 107579201B
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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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Abstract
The present invention relates to a multilayer body and a method for producing the same. The multilayer body includes a first reduced graphene oxide layer, a layer containing an electrochemically active material, and a second reduced graphene oxide layer, which are sequentially stacked. The electrode comprises the multilayer body. The multilayer body or the electrode is used for an electrochemical energy storage device, and the electrochemical energy storage device has good cycle performance and rate performance.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a multilayer body and a preparation method thereof.
Background
The lithium-sulfur battery uses sulfur or a sulfur-containing compound as a positive electrode and lithium or a lithium storage material as a negative electrode. The sulfur (S) used for the anode has the advantages of abundant resources, low price, safety, no toxicity, high theoretical specific capacity and the like.
CN103972467a discloses a multilayer composite positive electrode of a lithium-sulfur battery, which is formed by compounding four layers, and is sequentially as follows: a first graphene film layer, a carbon/sulfur active material layer, a second graphene film layer, and a polymer layer; wherein:
the first graphene film layer is obtained by dispersing graphene sheets in a solvent or a solvent containing a surfactant for 0.5-2h by ultrasonic, and then filtering to form a film;
the carbon/sulfur active material layer is formed by mixing elemental sulfur (serving as an active material), a carbon material and a binder in a weight ratio of (4-8): 1-5): 1;
the second graphene film layer is obtained by performing ultrasonic dispersion on graphene sheets in a solvent for 0.5-2 hours and then performing suction filtration on the graphene sheets to a polymer layer;
the polymer layer is a polypropylene microporous membrane, a polyethylene microporous membrane, a polyvinylidene fluoride (PVDF) membrane or a cellulose composite membrane with the pore size distribution range of 10-1000 nm.
Disclosure of Invention
The first aspect of the present invention provides a multilayer body including a first reduced graphene oxide layer, a layer containing an electrochemically active material, and a second reduced graphene oxide layer, which are sequentially stacked.
In one embodiment, the first reduced graphene oxide layer has a thickness of 1 μm or more, such as 1 to 10 μm, such as 2 to 5 μm; for example 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm.
In one embodiment, the electrochemically active material-containing layer has a thickness of 1 μm or more, for example, 1 to 1000 μm, for example, 1 to 200 μm.
In one embodiment, the thickness of the second reduced graphene oxide layer is 1 μm or more, e.g., 1 to 20 μm, e.g., 1 to 10 μm, e.g., 2 to 5 μm, e.g., 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm.
In one embodiment, the XPS C1s curve of reduced graphene oxide has the following characteristics:
if the XPS C1s curve is subjected to peak-splitting fitting, the curve can be divided into three peaks of a first peak, a second peak and a third peak, wherein the peak of the first peak is located at 284.5-285 eV (such as 284.7-284.9 eV, such as 284.8 eV), the peak of the second peak is located at 286.3-286.8 eV (such as 286.5-286.7 eV, such as 286.6 eV), and the peak of the third peak is located at 287.5-289 eV (such as 287.6-287.8 eV, such as 287.7 eV).
In one embodiment, after XPS C1s peak-split fitting of the reduced graphene oxide, the peak intensity of the first peak is 45% or more, such as 50% or more, such as 55% or more, such as 60% or more, such as 45-65% of the total peak intensity of the three peaks.
In one embodiment, the XPS C1s curve of the graphene oxide has the following characteristics:
if the XPS C1s curve is subjected to peak-splitting fitting, the curve can be divided into three peaks of a first peak, a second peak and a third peak, wherein the peak of the first peak is 284.5-285 eV (for example, 284.7-284.9 eV, for example, 284.8 eV), the peak of the second peak is 286.3-286.8 eV (for example, 286.5-286.7 eV, for example, 286.6 eV), and the peak of the third peak is 287.5-287.9 eV (for example, 287.6-287.8 eV, for example, 287.7 eV).
In one embodiment, the peak intensity of the first peak after XPS C1s peak-split fit of the graphene oxide is 40% or less, such as 36% or less, such as 25-35% of the total peak intensity of the three peaks.
In one implementation, after XPS C1s peak-split fitting of the reduced graphene oxide, the peak intensity of the oxygen-containing groups (e.g., C-O, C =o) accounts for less than 50%, preferably less than 40%, e.g., 39%, of the total peak intensity.
In one embodiment, peak intensity refers to the height of the peak.
In one embodiment, the first reduced graphene oxide layer or the second reduced graphene oxide layer is formed by stacking a plurality of single-layer reduced graphene oxides.
In one embodiment, the layer containing the electrochemically active material is an electrochemically active material layer.
In one embodiment, the layer containing the electrochemically active material is an electrochemical energy storage device active material layer.
In one embodiment, the layer containing the electrochemically active material is a battery active material layer.
In one embodiment, the layer containing the electrochemically active material is a battery positive electrode active material layer.
In one embodiment, the layer containing the electrochemically active material is a battery anode active material layer.
In one embodiment, the layer containing the electrochemically active material is a metal ion battery active material layer.
In one embodiment, the layer containing the electrochemically active material is a lithium ion battery active material layer.
In one embodiment, the layer containing the electrochemically active material is a lithium battery active material layer.
In one embodiment, the layer containing the electrochemically active material is a lithium sulfur battery active material layer.
In one embodiment, the layer containing an electrochemically active material is a lithium-sulfur battery positive electrode active material layer.
In one embodiment, the layer containing an electrochemically active material is a lithium sulfur battery anode active material layer.
The lithium sulfur battery active material (e.g., a lithium sulfur battery positive electrode active material or a lithium sulfur battery negative electrode active material) is any of the lithium sulfur battery active materials described in design high-energy lithium-sulfur batteries [ J ]. Chemical Society Reviews,2016,45 (20): 5605 ].
In one embodiment, the layer containing the electrochemically active material is a elemental sulfur layer.
In one embodiment, the layer containing the electrochemically active material is a layer containing a sulfur compound.
In one embodiment, the electrochemically active material is a sulfur-carbon composite.
In one embodiment, the electrochemically active material is a mixture of sulfur and graphene (e.g., graphene foam).
In one embodiment, the second layer contains a composite of sulfur and graphene (e.g., graphene foam).
In one embodiment, the layer containing the electrochemically active material is a sulfur-graphene foam composite layer. The sulfur-graphene foam composite material is a sulfur-graphene foam composite material described in Zhang K, xie K, yuan K, et al Enable effective polysulfide trapping and high sulfur loading via a pyrrole modified graphene foam host for advanced lithium-sulfur batteries [ J ]. Journal of Materials Chemistry A,2017.
In one embodiment, the layer containing an electrochemically active material is a secondary battery active material layer.
In one embodiment, the layer containing the electrochemically active material is a supercapacitor active material layer.
In one embodiment, the layer containing the electrochemically active material also contains a conductive agent and/or binder.
In yet another aspect, the invention provides an electrode comprising the multilayer body of any of the embodiments.
In yet another aspect, the invention provides an electrochemical energy storage device comprising at least two electrodes (e.g., a positive electrode and a negative electrode), at least one of the electrodes comprising a multilayer body.
In one embodiment, the electrochemical energy storage device further comprises a separator located between the two electrodes.
In one embodiment, the electrochemical energy storage device is a battery or supercapacitor;
in one embodiment, the electrochemical energy storage device is a lithium battery, such as a lithium sulfur battery.
In yet another aspect, the present invention provides a method of producing a multilayer body, comprising reducing graphene oxide on a layer containing an electrochemically active material, and forming a reduced graphene oxide layer on the layer containing the electrochemically active material.
In one embodiment, a method of preparing a multilayer body includes reducing graphene oxide on an active metal body, generating a first reduced graphene oxide layer on the active metal body, then compositing a layer containing an electrochemically active material on the first reduced graphene oxide layer, then reducing graphene oxide on the layer containing an electrochemically active material, generating a second reduced graphene oxide layer on the layer containing an electrochemically active material; and optionally removing the active metal body.
In one embodiment, the method of making a multilayer body comprises the steps of:
a) Immersing at least part (e.g., part) of one active metal body in a dispersion of graphene oxide, and compositing a first reduced graphene oxide layer on the active metal body;
b) Compounding (e.g., coating) a layer containing an electrochemically active material on the first reduced graphene oxide layer;
c) Immersing at least part (e.g. part) of the product of b) in a graphene oxide dispersion, compositing a second reduced graphene oxide layer on the electrochemically active material-containing layer;
alternatively, the process may be carried out in a single-stage,
d) Separating the active metal body from the product of step c) to obtain the multilayer body.
In one embodiment, in step c) of the method of producing a multilayer body, at least part of the active metal body and at least part of the layer containing the electrochemically active material are immersed in the graphene oxide dispersion.
In one embodiment, the method of making a multilayer body comprises the steps of:
a') floating the active metal body on the liquid surface of the dispersion liquid of the graphene oxide, and compositing a first reduced graphene oxide layer on the surface of the active metal body contacted with the dispersion liquid;
b') compositing (e.g., coating) a layer of electrochemically active material on the reduced graphene oxide layer;
c ') floating the product of step b') on the liquid surface of the dispersion of graphene oxide (e.g., contacting the active metal body and the electrochemically active material layer with the dispersion of graphene oxide), and compositing a second reduced graphene oxide layer on the electrochemically active material layer;
optionally also comprises
d ') separating the active metal body from the product of step c').
The inventors have found that when an active metal body is contacted with a dispersion of graphene oxide, the graphene oxide is capable of in situ reduction on the active metal body to produce reduced graphene oxide. The inventors have also found that when an active metal body, which is covered in this order with a first reduced graphene oxide layer and a layer containing an active material, is brought into contact with a graphene oxide dispersion, graphene oxide can be reduced in situ on the layer containing an electrochemically active material.
In one method of preparing a multilayer body, the graphene oxide dispersion is a dispersion of graphene oxide in a polar solvent;
in one method of producing a multilayer body, the graphene oxide dispersion is a dispersion of graphene oxide in water;
in a preparation method of a multilayer body, the concentration of graphene oxide in the graphene oxide dispersion liquid is 1-10 mg/L;
in a process for the preparation of a multilayer body, the graphene oxide dispersion has a pH of less than 7, preferably 4 to 6.
In one embodiment, a method of making a multilayer body produces a multilayer body according to any one of the present invention.
In one embodiment, the multilayer body according to any one of the present invention is produced by the production method of the above-described multilayer body.
In one embodiment, the active metal is, for example, magnesium, aluminum, zinc, iron, or tin.
The beneficial effects of the invention are that
The inventors have unexpectedly found that some embodiments of the present invention assemble a multilayer body using reduced graphene oxide layers that are less costly and simple to prepare, as compared to graphene layers that are more costly and difficult to prepare, the multilayer body being useful as an electrode for an electrochemical energy storage device, enabling efficient improvement in the performance of the electrochemical energy storage device.
The multilayer body of any of the embodiments of the invention has one or more of the following benefits:
the multilayer body of one or more embodiments serves as an electrode for an electrochemical energy storage device that exhibits one or more of the following benefits:
1) Higher specific capacity;
2) Higher cycle capacity retention;
3) Better multiplying power performance
4) Higher coulombic efficiency;
5) Lower internal resistance, in particular lower charge transfer impedance;
6) Lower cost;
7) The method for preparing the multilayer body is simple;
8) The method for preparing the multilayer body has low cost.
Drawings
FIG. 1 is a photograph of a composite electrode of example 1;
fig. 2 is an SEM photograph of the reduced graphene oxide layer of example 1;
FIG. 3 is an XRD diffraction pattern of a reduced graphene oxide sample and a GO sample;
fig. 4 (a) is C1s and O1s peaks of XPS spectra of Graphene Oxide (GO) and reduced graphene oxide (rGO);
fig. 4 (b) is a C1s spectrum of XPS spectra of Graphene Oxide (GO) and reduced graphene oxide (rGO);
FIG. 5 is a graph showing the cycle capacity curve and coulombic efficiency curve of the batteries of example 1 and comparative examples 1 to 2;
fig. 6 is a graph showing the rate discharge capacity of the batteries of example 1 and comparative examples 1 to 2;
fig. 7 shows ac impedance curves of the batteries of example 1 and comparative example 1.
Detailed Description
Reference will now be made in detail to specific embodiments of the invention. Examples of specific embodiments are illustrated in the accompanying drawings. While the invention will be described in conjunction with these specific embodiments, it will be understood that they are not intended to limit the invention to these specific embodiments. On the contrary, these embodiments are intended to cover alternatives, modifications and equivalents, which may be included within the spirit and scope of the invention as defined by the appended claims. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be practiced without some or all of these specific details. In other instances, well known process operations have not been described in detail in order not to unnecessarily obscure the present invention.
When used in conjunction with the description herein and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The sulfur powders used in the following examples were: chinese medicine sublimates sulfur CP (Shanghai test) more than or equal to 99.5%.
The method of preparing graphene foam is referred to as the method of the following documents: zhang K, xie K, yuan K, et al Enabled effective polysulfide trapping and high sulfur loading via a pyrrole modified graphene foam host for advanced lithium-sulfur bacteria [ J ]. Journal of Materials Chemistry A,2017.
Example 1
1. Adding 500mg of flake graphite into a mixed solution of sodium nitrate (500 mg) and concentrated sulfuric acid (46 ml), stirring and controlling the water bath temperature to be less than 10 ℃, continuously stirring and slowly adding potassium permanganate (3 g), and continuously stirring for 30 minutes;
the reaction solution is moved to a water bath with the temperature of 35 ℃ and is continuously stirred until the solution is gelatinous;
120ml of deionized water is added into the reaction solution, and then the reaction system is moved into a water bath with the temperature of 95 ℃ and stirred for 1 hour;
the reaction solution was moved to a room temperature atmosphere, and H having a mass fraction of 5% was dropwise added thereto 2 O 2 Stopping dripping the solution until no bubbles are generated in the reaction solution;
the reaction solution is filtered, the filter residue is washed by 1M dilute hydrochloric acid (500 ml), the pH of the washed waste liquid is more than 5 after the filter residue is sufficiently washed by ionized water, and the filter residue solid is subjected to ultrasonic treatment in water for 1 hour and then is subjected to freeze drying to obtain graphene oxide powder.
Dispersing graphene oxide powder in water to obtain graphene oxide powder with concentration of 2mg ml -1 Is a graphene oxide dispersion liquid.
2. A100 ml polytetrafluoroethylene-lined reactor (Teflon-lined Autoclave) was charged with 60ml of GO dispersion at a concentration of 2 mg/ml. And then sealing the reaction kettle, heating for 12 hours at 180 ℃, naturally cooling to room temperature, and freeze-drying the product in the reaction kettle to obtain a porous solid, namely graphene foam.
3. Weighing sulfur powder and graphene foam according to the mass ratio of 9:1, uniformly mixing in a mortar, then placing in a tube furnace, and under the atmosphere of nitrogen, standing at 10 ℃ for min -1 Heating to 155 ℃, preserving heat for 10 hours, and naturally cooling to room temperature to obtain the sulfur-graphene oxide composite material. And mixing the sulfur-graphene oxide composite material with an adhesive PVDF according to a mass ratio of 9:1, and then dissolving the mixture in an organic solvent NMP to obtain the anode slurry.
4. And (2) adjusting the pH value of the graphene oxide dispersion liquid in the step (1) to be 4 by hydrochloric acid, suspending the copper foil on the liquid surface of the graphene oxide dispersion liquid at room temperature, enabling one side surface of the copper foil to be in contact with the graphene oxide dispersion liquid, and enabling the other side surface of the copper foil to be exposed to air, and keeping the copper foil for 24 hours. The copper foil was then rinsed with deionized water and air dried at 60 ℃. And forming a reduced graphene oxide layer on the surface of the copper foil contacted graphene oxide dispersion liquid, namely obtaining a multilayer body I formed by sequentially laminating a copper layer and a first reduced graphene oxide layer.
5. And (3) coating the positive electrode slurry obtained in the step (3) on one side of a first reduced graphene oxide layer of the multilayer body I, and vacuum drying the product at 50 ℃ to obtain a multilayer body II formed by sequentially laminating a copper layer, the first reduced graphene oxide layer and a positive electrode material layer.
6. And (2) adjusting the pH value of the graphene oxide dispersion liquid in the step (1) to be 4 by hydrochloric acid, placing the multilayer body II in the solution at room temperature, suspending the multilayer body II on the liquid surface of the graphene oxide dispersion liquid, enabling one side surface of a positive electrode material layer of the multilayer body to be in contact with the graphene oxide dispersion liquid, exposing the other side surface of the positive electrode material layer of the multilayer body to air, and keeping the multilayer body II for 24 hours. The multilayer body was then removed and rinsed with deionized water and air dried at 60 ℃. And generating a reduced graphene oxide layer on one side of the positive electrode material layer of the multilayer body, namely obtaining a multilayer body III formed by sequentially laminating a copper layer, a first reduced graphene oxide layer, the positive electrode material layer and a second reduced graphene oxide layer.
7. The multilayer body III was immersed in dilute hydrochloric acid to separate the copper layer from the multilayer body, the multilayer body after peeling the copper layer was washed with deionized water, and then vacuum-dried at 55℃for 10 hours, to obtain a multilayer body IV formed by sequentially stacking a first reduced graphene oxide layer, a positive electrode material layer, and a second reduced graphene oxide layer, which is the composite electrode of example 1.
The total thickness of the multilayer body-IV was measured to be about 155-160 μm, the thickness of the first reduced graphene oxide layer was about 2-5 μm, the thickness of the positive electrode material layer was about 150 μm, and the thickness of the second reduced graphene oxide layer was about 2-5 μm.
Comparative example 1
The electrode of comparative example 1 was prepared as follows: mixing sulfur powder, conductive carbon black and a binder according to a weight ratio of 8:1:1, and then dissolving the mixture in an organic solvent NMP to obtain positive electrode slurry. And coating the positive electrode slurry on a copper foil, and vacuum drying to obtain the electrode of the comparative example 1.
Comparative example 2
(1) Positive electrode slurries were obtained in the same manner as in steps 1 to 3 of example 1.
(2) And (3) coating the positive electrode slurry on a copper foil, and vacuum drying the product at 50 ℃ to obtain a multilayer body-V formed by stacking a copper layer-positive electrode material layer.
(3) The graphene oxide dispersion of example 1 was adjusted to ph=4 with hydrochloric acid, and the multilayer body V was placed in the above solution at room temperature and suspended on the liquid surface of the graphene oxide dispersion, so that one surface of the positive electrode material layer of the multilayer body was in contact with the graphene oxide dispersion, and the other surface was exposed to air and kept for 24 hours. The multilayer body was then removed and rinsed with deionized water and air dried at 60 ℃. And forming a reduced graphene oxide layer on one side of the positive electrode material layer of the multilayer body, namely obtaining a multilayer body VI formed by sequentially laminating a copper layer, the positive electrode material layer and the reduced graphene oxide layer, wherein the multilayer body is the composite electrode of comparative example 2.
Analytical testing
1. Photograph of a person
Fig. 1 is a photograph of the composite electrode of example 1. The black surface in the figure is the surface of the second reduced graphene oxide layer. The figure illustrates that the second reduced graphene oxide layer was successfully composited on the positive electrode material layer.
2. SEM test
Scanning Electron Microscope (SEM) test was performed using a JSM-5612LV scanning electron microscope from FEI company, with an acceleration voltage of 10kV.
The reduced graphene oxide layer of multilayer-I was peeled off and stuck to a conductive adhesive to prepare an SEM sample, which was subjected to SEM test.
Fig. 2 is an SEM photograph of the reduced graphene oxide layer of example 1, in which the upper layer is the reduced graphene oxide layer, the thickness is about 2 μm, and the lower layer is the conductive paste, as indicated by the arrow in the figure.
3. XRD testing
The X-ray diffraction (XRD) test adopts diffractometer equipment model D/MAX-2400, and the test conditions are as follows: cu (K alpha) is used as radioactive source and the wavelength of X-rayThe voltage is 45kV, the scanning speed is 5 DEG/min, and the scanning range is 5-90 deg.
The reduced graphene oxide sample is the reduced graphene oxide peeled from the multilayer body I, and the GO sample is the graphene oxide powder obtained in the step 1.
Figure 3 shows XRD diffractograms of reduced graphene oxide and GO. The XRD diffraction pattern of the reduced graphene oxide has steamed bread peaks (peak value is about 24 degrees) in the range of 20-30 degrees. The XRD diffractogram of GO has sharp peaks at about 10 degrees.
4. XPS analysis
An X-ray photoelectron spectroscopy (XPS) analysis adopts an X-ray scanning microprobe electron spectrometer of the company Thermo Scientific, the model is Thermo Fisher K-Alpha, chemical bonds contained in elements in a material are measured, an X-ray source is an Al K Alpha microaggregation monochromator, the obtainable light spot size (30-400 mu m) is adopted, and the energy range of an ion gun is 100-4000eV.
Fig. 4 (a) is C1s peak and O1s peak of XPS spectra of Graphene Oxide (GO) and reduced graphene oxide (rGO). The ratio of C1s peak to O1s peak of reduced graphene oxide is higher than graphene oxide.
Fig. 4 (b) is a C1s spectrum of XPS spectra of Graphene Oxide (GO) and reduced graphene oxide (rGO), and peak-split fitting was performed on the C1s spectrum curve of fig. 4 using a gaussian fitting method. As can be seen from the figure, the C1s spectrum is divided into 3 peaks, representing 3 classes of C binding bonds, respectively: c=c/C-C (-284.8 eV), C-O (hydroxyl and epoxy, -286.6 eV), c=o (carbonyl, -287.7 eV). The intensity ratios of the peaks are as follows:
for GO, I (c=c/C-C): I (C-O): I (c=o) =2.74:3.88:1 (equivalent to 36%:51%: 13%);
for reduced graphene oxide, I (c=c/C-C): I (C-O): I (c=o) =9.32:4.57:1 (corresponding to 62%:31%: 7%).
From the above, it is clear that for reduced graphene oxide, a large number of oxygen-containing functional groups are eliminated, and the c=c/c—c bond becomes a host.
5. And (3) battery testing:
the electrodes of example 1 and comparative examples 1-2 were cut into round electrodes of 12mm diameter. The circular electrode is used as a positive electrode, and the lithium sheet is used as a negative electrode to assemble the lithium sulfur battery. The second graphene oxide layer of the composite electrode of example 1 was oriented toward the separator. The reduced graphene oxide layer of the composite electrode of comparative example 2 was oriented toward the separator.
The model number of the battery for test is 2032 button battery. The sulfur loading per unit area of the electrode of comparative example 1 was about 0.88mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The sulfur loading per unit area of the electrodes of comparative example 2 and example 1 was about 6mg/cm 2 . The battery separator was Celgard PP. The electrolyte of the battery is LiTFSI (1M) +1wt% LiNO 3 Dissolved in DOL, dme=1:1 (V/V).
(1) Cycle capacity test
The battery test equipment is an Arbin 88 channel, constant current charge and discharge is carried out, and the test current is 0.2C; the test voltage range is 1.5-3V. FIG. 5 is a graph showing specific discharge capacity and coulombic efficiency of example 1 and comparative examples 1 to 2. Table 1 shows the specific discharge capacities and coulombic efficiencies of example 1 and comparative examples 1 to 2.
TABLE 1
(2) Multiplying power test
The batteries of example 1 and comparative examples 1 to 2 were also subjected to charge and discharge tests at different rates. Sequentially using 0.2C, 0.5C, 1C, 2C, 5C, and 0.2C, each cycle was performed for 10 weeks. Fig. 6 is a graph showing discharge capacity curves of the batteries of example 1 and comparative examples 1 to 2 at different rates.
(2) AC impedance testing
The alternating current impedance spectrum of an electrochemical workstation test electrode of SI-1287 model of British power transmission is precisely measured, the test conditions are all carried out at room temperature, the test frequency range is 0.05 Hz-100 kHz, and the amplitude of disturbance sinusoidal voltage is 10mV.
Fig. 7 shows ac impedance curves of the batteries of example 1 and comparative example 1. The Z 'of the cell of example 1 was about 34.33 and the Z' of the cell of comparative example 1 was about 4769.85. It can be seen that the battery of example 1 has a lower charge transfer impedance and thus lower internal resistance and better electrochemical performance.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same; while the invention has been described in detail with reference to the preferred embodiments, those skilled in the art will appreciate that: modifications may be made to the specific embodiments of the present invention or equivalents may be substituted for part of the technical features thereof; without departing from the spirit of the invention, it is intended to cover the scope of the invention as claimed.
Claims (17)
1. A multilayer body comprising a first reduced graphene oxide layer, an electrochemically active material-containing layer, and a second reduced graphene oxide layer, which are sequentially stacked, prepared by a method comprising the steps of:
a) Immersing at least part of an active metal body into a dispersion liquid of graphene oxide, reducing the graphene oxide on the active metal body, generating a first reduced graphene oxide layer on the active metal body,
b) A layer containing an electrochemically active material is composited on the first reduced graphene oxide layer,
c) Immersing at least part of the active metal body and at least part of the electrochemically active material-containing layer of the product of b) in a graphene oxide dispersion, reducing graphene oxide on the electrochemically active material-containing layer, generating a second reduced graphene oxide layer on the electrochemically active material-containing layer,
wherein the active metal body is copper, magnesium, aluminum, zinc, iron or tin, and the graphene oxide dispersion liquid is a dispersion liquid of graphene oxide in water.
2. The multilayer body according to claim 1, wherein the first reduced graphene oxide layer or the second reduced graphene oxide layer is formed by stacking a plurality of single-layer reduced graphene oxides.
3. The multilayer body of claim 1 having one or more of the following features:
-the first reduced graphene oxide layer has a thickness of 1 μm or more;
-the thickness of the layer containing electrochemically active material is 1 μm or more;
-the thickness of the second reduced graphene oxide layer is 1 μm or more.
4. The multilayer body of claim 1 having one of the following features:
-the layer containing an electrochemically active material is a battery active material layer;
-the layer containing electrochemically active material is a metal ion battery active material layer;
-the layer containing electrochemically active material is a lithium ion battery active material layer;
-the layer containing an electrochemically active material is a lithium-sulfur battery active material layer;
-the layer containing an electrochemically active material is a elemental sulphur layer;
-the layer containing an electrochemically active material is a layer of a sulphur-carbon composite material;
-the layer containing an electrochemically active material is a sulphur-graphene foam composite layer;
-the layer containing electrochemically active material is a supercapacitor active material layer.
5. An electrode comprising the multilayer body according to any one of claims 1 to 4.
6. An electrochemical energy storage device comprising the multilayer body of any one of claims 1-4.
7. An electrochemical energy storage device as in claim 6, comprising at least two electrodes, at least one electrode comprising the multilayer body of any one of claims 1-4.
8. An electrochemical energy storage device as in claim 7, further comprising a separator positioned between the two electrodes.
9. An electrochemical energy storage device as in claim 8, which is a battery or supercapacitor.
10. An electrochemical energy storage device as in claim 9, which is a lithium sulfur battery.
11. A method of making a multilayer body comprising:
a) Immersing at least part of an active metal body into a dispersion liquid of graphene oxide, reducing the graphene oxide on the active metal body, generating a first reduced graphene oxide layer on the active metal body,
b) A layer containing an electrochemically active material is composited on the first reduced graphene oxide layer,
c) Immersing at least part of the active metal body and at least part of the electrochemically active material-containing layer of the product of b) in a graphene oxide dispersion, reducing graphene oxide on the electrochemically active material-containing layer, generating a second reduced graphene oxide layer on the electrochemically active material-containing layer,
wherein the active metal body is copper, magnesium, aluminum, zinc, iron or tin, and the graphene oxide dispersion liquid is a dispersion liquid of graphene oxide in water.
12. The method of manufacturing of claim 11, further comprising: separating the active metal body from the product of step c).
13. The preparation method according to claim 11, wherein in the step b), a layer containing an electrochemically active material is coated on the reduced graphene oxide layer.
14. The production method according to claim 11, wherein the concentration of graphene oxide in the graphene oxide dispersion liquid is 1 to 10mg/L.
15. The method of claim 11, wherein the graphene oxide dispersion has a PH of less than 7.
16. The production method according to claim 15, wherein the graphene oxide dispersion has a PH of 4 to 6.
17. The production method according to any one of claims 11 to 16, wherein the multilayer body is a multilayer body according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN109888176B (en) * | 2019-01-22 | 2020-12-01 | 浙江工业大学 | Positive electrode of lithium-sulfur secondary battery |
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