CN114094096B - Method for forming protective polymer film on surface of sodium titanium phosphate negative electrode material, product and application thereof - Google Patents
Method for forming protective polymer film on surface of sodium titanium phosphate negative electrode material, product and application thereof Download PDFInfo
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- CN114094096B CN114094096B CN202111341483.8A CN202111341483A CN114094096B CN 114094096 B CN114094096 B CN 114094096B CN 202111341483 A CN202111341483 A CN 202111341483A CN 114094096 B CN114094096 B CN 114094096B
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 method for forming a protective polymer film on the surface of a sodium titanium phosphate anode material, a product and application thereof, wherein the method comprises the steps of adding a functional additive into electrolyte and preparing NaTi based on an electrochemical modification method 2 (PO 4 ) 3 The protective polymer film is formed on the surface of the negative electrode, and the modified negative electrode is used in a water-based sodium ion battery, so that the coulombic efficiency of nearly 100 percent, and the charge-discharge rate performance and the cycle stability are excellent. Compared with the original electrode, the modified electrode surface forms a layer of protective polymer film, the film layer can be similar to an SEI film in a traditional lithium ion battery, normal transmission of sodium ions is not hindered, direct contact of a negative electrode active substance and electrolyte can be blocked, interface stability of a negative electrode is further enhanced, utilization rate of the negative electrode active substance is improved, good multiplying power characteristics and cycle performance are shown, and the film layer has a good application prospect in an electrochemical energy storage battery technology.
Description
Technical Field
The invention relates to the technical field of chemical power supplies, in particular to a method for forming a protective polymer film on the surface of a sodium titanium phosphate negative electrode material, a product and application thereof.
Background
In recent years, development of renewable clean energy sources such as wind energy, solar energy and tidal energy is emphasized, but the renewable clean energy sources have discontinuity and instability in the process of converting the renewable clean energy sources into electric energy, which is not beneficial to safe operation of a grid after grid connection. The application of the energy storage technology is an effective way for realizing high-efficiency conversion and stable output of electric energy, and can obviously improve the level of the renewable energy sources, support distributed electric power and a microgrid. The water-based sodium ion battery has the advantages of high safety, low raw material cost, wide sodium element distribution, green environment protection and the like, receives more and more research attention, and achieves great progress. Because the energy storage and conversion of the sodium ion battery occur in the anode and cathode materials, the key point of developing a long-life battery is to prepare an electrode material capable of stably removing and embedding Na ions. However, it is not easy to find a negative electrode material suitable for stably deintercalating Na in such a battery, which is one of the difficulties that the development of aqueous sodium ion batteries needs to be mainly solved.
The negative electrode systems currently considered suitable are mainly activated carbon and NaTi 2 (PO 4 ) 3 . However, the application of the activated carbon material is limited by the defects of large irreversible capacity, low energy density and the like. NaTi (NaTi) 2 (PO 4 ) 3 The material is a sodium fast ion conductor, has the advantages of fast Na insertion and removal, stable structure, stable charge and discharge platform and the like, and has good application prospect in the field of water-based sodium ion batteries. However, at low magnification<1C) During long-time running of batteries such as circulation or deep charge and discharge, naTi 2 (PO 4 ) 3 The negative electrode is easy to have serious capacity attenuation, resulting in NaTi 2 (PO 4 ) 3 The charge-discharge cycle stability of the negative electrode is poor, which becomes a key factor restricting the battery application.
Due to NaTi 2 (PO 4 ) 3 The anode material is easy to be combined with H in electrolyte 2 O、O 2 Or OH-or the like, and therefore, naTi is to be raised 2 (PO 4 ) 3 The cycle stability of the negative electrode is required to suppress side reactions occurring at the interface of the negative electrode and to improve the chemical stability of the negative electrode in the electrolyte. In order to improve the chemical stability of the cathode in the electrolyte, a currently common approach is carbon coating, which is generally based on decomposition of carbon materials or organic matters in the precursor under inert atmosphere to form a coating on NaTi 2 (PO 4 ) 3 A carbon layer on the surface of the particles, which on the one hand can hinder the NaTi 2 (PO 4 ) 3 The aggregation of the particles grows up, shortens the electron transmission path, forms a conductive network, improves the conductivity of the material, and can isolate NaTi on the other hand 2 (PO 4 ) 3 And the particles are in direct contact with the electrolyte, so that the side reaction of the interface is avoided. Further, based on similar ideas, there are also those in the NaTi 2 (PO 4 ) 3 A small amount of polypyrrole conductive polymer is added into the negative electrode, and a conductive coating is formed on the surface of the negative electrode, so that the cycle stability of the negative electrode is improved. However, the above method is difficult to achieve uniform coating and to effectively inhibit the penetration of the electrolyte, thereby making it difficult to avoidAnd interface side reactions are avoided. Therefore, in order to improve the interfacial stability of the anode, a method of forming a negative electrode on the NaTi 2 (PO 4 ) 3 Method for forming protective polymer film on surface of negative electrode material, thereby blocking direct contact between negative electrode material and electrolyte, enhancing interface stability of negative electrode, and improving NaTi 2 (PO 4 ) 3 The charge-discharge cycle performance of the cathode promotes the commercial application of the cathode.
Thus, naTi 2 (PO 4 ) 3 The charge-discharge cycle stability of the cathode material is poor, and simultaneously NaTi 2 (PO 4 ) 3 The negative electrode material is easy to generate some interface side reactions with electrolyte to influence the interface stability of the negative electrode, which is a technical problem to be solved by the technicians in the field.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a method for forming a protective polymer film on the surface of a sodium titanium phosphate anode material, a product and application thereof.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
a method for forming a protective polymer film on the surface of a sodium titanium phosphate anode material, comprising the following steps:
(1) Carbon-coated modified NaTi 2 (PO 4 ) 3 Uniformly mixing (NTP/C) active materials, a conductive agent and a binder according to a certain mass ratio, and coating the mixture on a current collector to prepare an NTP/C negative plate serving as a negative substrate for standby; the NaTi 2 (PO 4 ) 3 The mass ratio of the (NTP/C) active material to the conductive agent to the binder is as follows: 6-8:1-3:0.5-1.5, preferably 7:2:1, a step of;
(2) Preparing a composite plating solution, wherein the composite plating solution comprises an inorganic sodium salt aqueous solution and a functional additive solution;
(3) Placing the negative electrode substrate into a composite plating solution for constant potential electrochemical surface modification, and performing electrochemical deposition on the surface of the negative electrode substrate to obtain a protective polymer film;
as a preferable mode of the invention, naTi in the step (1) 2 (PO 4 ) 3 The preparation method of the (NTP/C) active material comprises the following steps:
(1.1) dissolving sodium carbonate, ammonium dihydrogen phosphate and citric acid in deionized water to obtain a solution A;
(1.2) dissolving tetrabutyl titanate in ethanol to obtain a solution B;
(1.3) pouring the solution B into the solution A, stirring and drying to obtain a precursor;
(1.4) preheating the precursor at 330-380 ℃ for 3-4 h, and then sintering at 750-850 ℃ for 10h to obtain the carbon-coated modified NaTi 2 (PO 4 ) 3 (NTP/C) active material.
As a preferable mode of the invention, the NaTi 2 (PO 4 ) 3 The (NTP/C) active material contains carbon of not more than 10%; the NaTi 2 (PO 4 ) 3 The (NTP/C) active material is in the form of granule, and the granule diameter is not more than 10 μm.
As a preferable scheme of the invention, the conductive agent is one or more of Super P carbon black, acetylene black, carbon nano tube, graphene, titanium dioxide and the like; the binder can be one or more of PVDF, PTFE, CMC, SBR and the like; the current collector can be one or more of aluminum foil, titanium mesh, stainless steel mesh and the like.
As a preferable scheme of the invention, the temperature of the composite plating solution in the step (3) is 10-40 ℃ in the electrochemical process, and the electrode potential (relative to SCE) is not more than 1.2V; the functional additive in the composite plating solution is one or more of pyrrole monomer (PY), aniline monomer (AN), vinylene Carbonate (VC), carboxymethyl cellulose (CMC) and Agarose (AG). The volume ratio or mass ratio of the functional additive in the aqueous solution is not more than 1%, and the concentration of the inorganic sodium salt aqueous solution is preferably 1.0 mol.L -1 。
The product is prepared by adopting the method for forming the protective polymer film on the surface of the sodium titanium phosphate anode material. The product is modified NTP/C negative electrode, namely NaTi 2 (PO 4 ) 3 And a negative electrode. In NaTi 2 (PO 4 ) 3 Protective polymer formed on surface of negative electrode materialMethod for preparing film for blocking NaTi 2 (PO 4 ) 3 Direct contact of the negative electrode and the electrolyte can inhibit interface side reaction between the negative electrode and the electrolyte, so that the interface stability of the negative electrode is improved, and the problem of NaTi is solved 2 (PO 4 ) 3 The charge-discharge cycle stability of the cathode material is poor. The modified NTP/C negative electrode is used as a working electrode, a platinum sheet is used as a counter electrode and Saturated Calomel (SCE) is used as a reference electrode, the aqueous solution is used as electrolyte, a three-electrode electrolytic cell device is constructed, and a half-cell charge-discharge test of the negative electrode of the aqueous sodium ion battery is performed.
A sodium ion battery comprising an electrolyte, a positive electrode and a negative electrode, wherein the negative electrode is prepared by the method for forming a protective polymer film on the surface of the sodium titanium phosphate negative electrode material according to any one of claims 1 to 9. The electrolyte in the electrolyte is Li 2 SO 4 、Na 2 SO 4 And K 2 SO 4 The solvent of the electrolyte is water.
The beneficial effects of the invention are as follows: according to the invention, the functional additive is added into the electrolyte, and the protective polymer film can be formed on the surface of the NTP/C negative electrode based on an electrochemical modification method, so that the modified negative electrode is used in a water-based sodium ion battery, and the negative electrode can show coulombic efficiency close to 100%, excellent charge-discharge rate performance and cycle stability. Compared with the original electrode, the modified electrode surface forms a layer of protective polymer film, and the film layer is similar to an SEI film in a traditional lithium ion battery, can not obstruct normal transmission of sodium ions, can block direct contact of a negative electrode active substance and electrolyte, further enhance interface stability of a negative electrode, improve utilization rate of the negative electrode active substance, show good multiplying power characteristics and cycle performance, and has good application prospect in the electrochemical energy storage battery technology.
The invention will be further described with reference to the drawings and examples.
Drawings
FIG. 1 is a surface scanning electron microscope image of the original NTP/C negative electrode in example 1.
FIG. 2 is a surface scanning electron microscope image of the NTP/C negative electrode after the modification treatment in example 1.
FIG. 3 shows the charge and discharge performance of the modified anode of example 1 at different rates, with a test voltage range of 0-1.0V vs.
FIG. 4 is a graph showing the cycling performance of the modified negative electrode of example 1 at a 2C rate, with a test voltage range of 0-1.0V vs.
FIG. 5 is a graph showing the cycling performance of the modified negative electrode of example 1 at 5C rate, with a test voltage range of 0-1.0V vs.
Detailed Description
The following examples merely illustrate the invention in further detail, but do not constitute any limitation thereof.
Example 1, the method for forming a protective polymer film on the surface of a sodium titanium phosphate anode material provided in this example: carbon-coated modified NaTi 2 (PO 4 ) 3 The (NTP/C) active material, conductive carbon black (Super P) and a binder (PTFE) are mixed according to the mass ratio of 7:2:1, dissolving in a proper amount of deionized water, uniformly mixing, rolling to form a film, then drying in vacuum, cutting into electrode slices by using a slicer, putting the electrode slices on a titanium net to form an NTP/C electrode, weighing and calculating the mass of active substances to obtain the NTP/C negative electrode substrate.
At Na (Na) 2 SO 4 In +0.5vol.% PY electrolyte, performing electrochemical oxidation modification on the NTP/C negative electrode surface by using a potentiostatic polarization method to obtain a protective polymer film by electrochemical deposition on the electrode surface, wherein the oxidation potential is 0.9V, and the oxidation time is 30min to obtain a modified NTP/C negative electrode, namely NaTi 2 (PO 4 ) 3 And a negative electrode.
Example 2: the method for forming a protective polymer film on the surface of a sodium titanium phosphate anode material provided in this example is substantially the same as that of example 1, except that the carbon-coated modified NaTi 2 (PO 4 ) 3 The (NTP/C) active material, conductive carbon black (Super P) and a binder (PTFE) are mixed according to the mass ratio of 6:1:0.5.
example 3: the embodiment provides a method for forming a protective property on the surface of a sodium titanium phosphate anode materialThe polymer film process, which is essentially the same as example 1, differs in that the carbon-coated modified NaTi 2 (PO 4 ) 3 The (NTP/C) active material, conductive carbon black (Super P) and a binder (PTFE) are mixed according to the mass ratio of 8:3:1.5.
example 4: the method for forming a protective polymer film on the surface of a sodium titanium phosphate anode material provided in this example is substantially the same as that of example 1, except that the carbon-coated modified NaTi 2 (PO 4 ) 3 The (NTP/C) active material, conductive carbon black (Super P) and a binder (PTFE) are mixed according to the mass ratio of 7.5:2.6:1.3.
for the sake of space, the modified NTP/C negative electrode obtained in example 1, naTi, is used alone 2 (PO 4 ) 3 The negative electrode is used for application description. The modified NTP/C negative electrode is used as a working electrode, a platinum sheet is used as a counter electrode and Saturated Calomel (SCE) is used as a reference electrode, 1.0mol.L -1 Na of (2) 2 SO 4 And (3) taking the solution as electrolyte, constructing a three-electrode electrolytic cell device, and performing a half-cell charge-discharge test of the negative electrode of the water-based sodium ion battery.
Microscopic morphology analysis was performed on the NTP/C negative electrode surface before and after oxidative modification obtained in this example 1 using Scanning Electron Microscopy (SEM), as shown in fig. 1 and 2. Compared with the surface morphology of the original NTP/C negative electrode, the surface morphology of the electrode after oxidation modification is obviously changed, which shows that a protective polypyrrole film with better compactness can be generated on the surface of the NTP/C negative electrode, and the polypyrrole particles are spherical. Meanwhile, the surface scanning component analysis is carried out on the modified NTP/C electrode surface by utilizing an X-ray energy scattering spectrum (EDS), the N element contained on the electrode surface can be obviously detected, and further, the protective polypyrrole film is formed on the NTP/C electrode surface.
Fig. 3 shows charge and discharge curves of NTP/C negative electrode at different rates, and it can be seen from fig. 3 that when the charge and discharge rate is not more than 5C, the discharge capacity of the modified NTP/C electrode in example 1 is significantly higher than that of the original NTP/C electrode, but when the charge and discharge rate is as high as 10C, the capacity of the modified NTP/C electrode is lower than that of the original electrode, which may be due to that the volume structure of the surface polypyrrole protective film is easily damaged by the excessively high discharge current density. Fig. 4 also shows the charge-discharge cycle curve of the NTP/C negative electrode at 2C magnification, and it can be seen that the charge-discharge coulombic efficiency of the modified electrode is about 95%, which is significantly higher than that of the original electrode (about 80%), and the capacity of the modified electrode is still higher than that of the original electrode after 150 cycles. Further, fig. 5 shows the charge-discharge cycle curve of the NTP/C negative electrode at 5C magnification, and it can also be seen that the charge-discharge coulombic efficiency of the modified electrode is about 95%, significantly higher than that of the original electrode (about 70%), and the capacity retention rate of the modified electrode after 500 cycles is about 46%, higher than that of the original electrode (about 30%).
The result shows that the charge-discharge coulomb efficiency, the discharge capacity and the cycle stability of the modified NTP/C negative electrode are obviously superior to those of the original electrode, and the modified NTP/C negative electrode is mainly characterized in that a polypyrrole protective film (about 20-25 mu m thick) is formed on the surface of the modified electrode, and the film layer is similar to an SEI film in a lithium ion battery, so that normal transmission of sodium ions is not blocked, and meanwhile, the direct contact of a negative electrode active substance and an electrolyte can be blocked, so that the interface stability of the negative electrode is enhanced, and the multiplying power characteristic and the cycle performance of the negative electrode are improved. It is notable, however, that the discharge capacity of the modified electrode significantly exceeds that of NaTi at lower rates 2 (PO 4 ) 3 Theoretical specific capacity of active material (133 mAh.g) -1 ) This is probably due to the fact that the polypyrrole protective film on the electrode surface is subject to SO 4 2- The deintercalation reaction of the ions in the film layer shows a certain capacitance characteristic, thereby providing additional specific discharge capacity.
Variations and modifications to the above would be obvious to persons skilled in the art to which the invention pertains from the foregoing description and teachings. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are used for convenience of description and are not intended to limit the present invention in any way, and other methods using the same or similar methods are within the scope of the present invention.
Claims (7)
1. A method for forming a protective polymer film on the surface of a sodium titanium phosphate anode material, which is characterized in that: which comprises the following steps:
(1) Carbon-coated modified NaTi 2 (PO 4 ) 3 Uniformly mixing (NTP/C) active material, conductive agent and binder according to a certain mass ratio, and coating on a current collector to prepare a negative plate which is used as a negative substrate for standby;
(2) Preparing a composite plating solution, wherein the composite plating solution comprises an inorganic sodium salt aqueous solution and a functional additive solution;
(3) Placing the negative electrode substrate into a composite plating solution for constant potential electrochemical surface modification, and performing electrochemical deposition on the surface of the negative electrode substrate to obtain a protective polymer film;
the carbon-coated modified NaTi in the step (1) 2 (PO 4 ) 3 The preparation method of the (NTP/C) active material comprises the following steps:
(1.1) dissolving sodium carbonate, ammonium dihydrogen phosphate and citric acid in deionized water to obtain a solution A;
(1.2) dissolving tetrabutyl titanate in ethanol to obtain a solution B;
(1.3) pouring the solution B into the solution A, stirring and drying to obtain a precursor;
(1.4) sintering the precursor at high temperature to obtain carbon-coated modified NaTi 2 (PO 4 ) 3 (NTP/C) active material;
the carbon-coated modified NaTi 2 (PO 4 ) 3 The (NTP/C) active material contains carbon of not more than 10%; the NaTi 2 (PO 4 ) 3 The (NTP/C) active material is granular, and the grain diameter is not more than 10 mu m;
the temperature of the composite plating solution in the step (3) is 10-40 ℃ during electrochemical surface modification, and the electrode potential is not more than 1.2V; the functional additive in the composite plating solution is one or more of pyrrole monomer, aniline monomer and vinylene carbonate.
2. The method for forming a protective polymer film on the surface of a sodium titanium phosphate anode material according to claim 1, wherein: the carbon-coated modified NaTi 2 (PO 4 ) 3 The mass ratio of the (NTP/C) active material to the conductive agent to the binder is as follows: 6-8:1-3:0.5-1.5.
3. The method for forming a protective polymer film on the surface of a sodium titanium phosphate anode material according to claim 1, wherein: in the step (1.4), the precursor is preheated at 330-380 ℃ for 3-4 h, and then sintered at 750-850 ℃ for 10-h.
4. The method for forming a protective polymer film on the surface of a sodium titanium phosphate anode material according to claim 1, wherein: the conductive agent is one or more of Super P carbon black, acetylene black, carbon nanotubes, graphene and titanium dioxide; the adhesive is one or more of PVDF, PTFE, CMC, SBR; the current collector is one or more of aluminum foil, titanium mesh and stainless steel mesh.
5. An article made by the method of any one of claims 1-4 for forming a protective polymer film on the surface of a sodium titanium phosphate negative electrode material.
6. A sodium ion battery comprising an electrolyte, a positive electrode and a negative electrode, wherein the negative electrode is prepared by the method for forming a protective polymer film on the surface of a sodium titanium phosphate negative electrode material according to any one of claims 1 to 4.
7. The sodium ion battery of claim 6 wherein: the electrolyte in the electrolyte is Li 2 SO 4 、Na 2 SO 4 And K 2 SO 4 The solvent of the electrolyte is water.
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