CN116477593A - High-stability high-conductivity composite titanium phosphorus oxide and preparation method thereof - Google Patents

High-stability high-conductivity composite titanium phosphorus oxide and preparation method thereof Download PDF

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CN116477593A
CN116477593A CN202210045277.0A CN202210045277A CN116477593A CN 116477593 A CN116477593 A CN 116477593A CN 202210045277 A CN202210045277 A CN 202210045277A CN 116477593 A CN116477593 A CN 116477593A
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titanium
sodium
phosphorus oxide
phosphate
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CN116477593B (en
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侯肖瑞
贺诗阳
田剑莉亚
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Taicang Zhongkoseno New Energy Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract

A high-stability high-conductivity composite titanium phosphorus oxide and a mass production method thereof. The composite titanium phosphorus oxide adopts a second phase as a stable phase, so that the ion transmission conductance and the chemical stability can be greatly improved; the coating phase generated in the sintering process of the water-soluble carbon-containing substances added into the raw materials ensures high electronic conductivity, and the water-soluble carbon-containing substances do not need to be additionally mixed with carbon materials in the preparation of the later-stage electrode.

Description

High-stability high-conductivity composite titanium phosphorus oxide and preparation method thereof
Technical Field
The invention relates to a high-stability high-conductivity composite titanium phosphorus oxide and a preparation method thereof, and also relates to a water-based ion battery.
Background
Intermittent renewable energy sources represented by solar energy and wind energy are connected into a power grid through storage and release of an energy storage system, so that a large-scale energy storage technology is a foundation for new energy popularization and energy innovation. The application has very strict requirements on battery technology, high safety performance, long cycle life, low electricity cost and wide temperature adaptability.
The most widely used electrochemical energy storage technologies to date are Lithium Ion Battery (LIB) and Lead Acid Battery (LAB) technologies. However, for energy storage systems, LIB cannot maintain a high cycle life at all in high temperature applications, and moreover the risk of LIB thermal runaway requires complex systems, high costs and high operating expenses to ensure the safety of the system (1); LABs cannot achieve long cycle life at high depth of charge (DOD), and LAB's high temperature resistance is even worse than LIB (2). More importantly, the energy storage application of the large-scale integration (MWh class or more) has the characteristics of large investment, long operation and maintenance period and the like, is influenced by the consistency of batteries, difficulty in integrated modular control and the like, and has a series of energy storage system and power station combustion accidents in the world in recent years, so that the intrinsic safety of the batteries still needs to be highly valued, and the problem of the large-scale popularization and urgent need to be solved of the energy storage batteries at present is also solved.
The water-based ion battery adopts neutral saline water solution as electrolyte, so that the problem of flammability of organic electrolyte is avoided, the defects of high pollution, short service life (such as a lead-acid battery) and high price (a nickel-hydrogen battery) of the traditional water-based battery are overcome, the water-based ion battery has the characteristics of safety, low cost, long service life, environment friendliness, recoverability and the like, and is a brand-new novel battery and an ideal system for large-scale energy storage technology.
The water system sodium ion battery is one of the energy storage batteries with the most investment potential because of the advantages of low cost, long cycle life, high safety, environmental protection and the like. One core bottleneck for restricting the development and scale application of the water-based sodium-ion battery is the stability and maturity of the negative electrode material, and due to the advantages of high stability, low cost and the like of the sodium-ion intercalation-deintercalation structure, the NASICON structure titanium phosphorus oxide NaTi x M y (PO 4) 3 (m=ti, V, mn, x+y=2) is considered as the sodium-ion battery anode active material most promising for application. Advantages include relatively high specific capacity, excellent thermal stability, low manufacturing cost, suitable redox potential; at the same time, these materials also have certain disadvantages: 1) The material itself has low electron conductivity; 2) The material itself has low ionic conductivity; 3) Is sensitive to pH environment, and is sensitive to alkaline solution (pH>12 A sharp increase in dissolution rate, leading to attenuation; to realize water systemThe sodium ion battery has high energy density and long cycle life, and the conductivity and stability of the negative electrode material of the water-based sodium ion battery must be improved.
Disclosure of Invention
The main content of the invention is high-stability high-conductivity composite titanium phosphorus oxide and a mass production method thereof. The composite titanium phosphorus oxide adopts a second phase as a stable phase, so that the ion transmission conductance and the chemical stability can be greatly improved; the coating phase generated in the sintering process of the water-soluble carbon-containing substances added into the raw materials ensures high electronic conductivity, and the water-soluble carbon-containing substances do not need to be additionally mixed with carbon materials in the preparation of the later-stage electrode.
Drawings
FIG. 1 is an EIS pattern of examples and comparative examples.
FIG. 2 is an accelerating cycle curve for examples and comparative examples.
Fig. 3 is SEM microtopography after corrosion resistance testing of examples and comparative examples.
Detailed Description
The invention mainly relates to a high-stability and high-conductivity composite titanium phosphorus oxide and a mass production method thereof, and specifically comprises the following characteristics:
1. the composite titanium phosphorus oxide is composed of a main phase, a stable phase and a coating phase.
2. The main phase is NASICON structure titanium phosphorus oxide NaTi x M y (PO 4 ) 3 Where m=ti, V, mn, x+y=2.
3. The stable phase includes two of the following: one is M 0.5 Ti 2 (PO 4 ) 3 (m= Sr, ca, mn, mg, co, cu); two are M 1 (TiM 2 )(PO 4 ) 3 ，M 1 ＝Fe、Na、Mn、Sn、Na，M 2 ＝Ge、Nb、Cr、Sn。
4. The coating phase is a hydrophilic amorphous carbon material and is formed by high-temperature decomposition and carbonization of liquid-phase carbonized raw materials under inert atmosphere, wherein the liquid-phase carbonized raw materials comprise, but are not limited to, polydopamine, resorcinol-formaldehyde resin, saccharides (glucose, sucrose or fructose), polyvinylpyrrolidone (PVP), tannic acid, citric acid, polyvinyl alcohol, polypyrrole, vitamin C, polyethylene glycol and the like.
5. The content of the stable phase is 0.01-1.0wt.%.
6. The content of the coating phase is 0-3wt.%.
7. The thickness of the coating phase is 2-50nm.
The preparation method provided by the invention is characterized by comprising the following specific steps:
1. the sodium source is at least one of sodium phosphate, sodium carbonate, sodium dihydrogen phosphate, sodium hydroxide and sodium acetate, and the primary particle diameter D50 is less than 3 μm.
2. The titanium source is at least one of titanium dioxide, titanium hydroxide, meta-titanic acid and tetrabutyl titanate, and the primary particle diameter D50 is smaller than 1 mu m.
3. The phosphorus source is at least one of phosphoric acid, monoammonium phosphate, diammonium phosphate, ammonium phosphate, sodium dihydrogen phosphate and disodium hydrogen phosphate, and the primary particle diameter D50 is less than 3 μm.
4. Inorganic salts corresponding to the metal cations thereof are selected as raw materials according to the kind of the added stable phase, and include, but are not limited to, carbonates, phosphates, acetates, etc.
5. If the original material is insoluble in water and the particle size does not meet the requirement, adopting a crushing mode for pretreatment, wherein the crushing method comprises, but is not limited to, mechanical crushing, air flow crushing and ultrasonic crushing; the crushing form includes crushing the material directly or crushing in solvent.
6. The solvent selected in the preparation process is water.
7. No matter what preparation method is adopted, a titanium source is required to be added in the preparation process, and a sodium source and a phosphorus source are sequentially added after uniform dispersion.
8. The coating phase is added in the form of liquid-phase charrable raw materials, and the addition amount is calculated according to the high-temperature charring residual rate of different raw materials. The molar ratio of the addition amount of the coating phase to the metal ions is 1:1 to 5:1.
9. the ph=6-8 of the slurry/mixed material needs to be adjusted according to different material sources in the preparation process.
The pH value is regulated by adopting hydroxide corresponding to metal cation or inorganic acid corresponding to anion.
11. And drying the slurry, and sintering the slurry in an inert atmosphere.
12. Drying techniques include, but are not limited to, spray drying, microwave drying, and the like.
13. Inert atmospheres include, but are not limited to, helium, nitrogen, argon, and the like.
14. The sintering temperature is 600-1000 ℃ and the sintering time is 5-20 hours.
In one embodiment, the composite titanium phosphorus oxide of the present invention is comprised of a main phase, a stable phase and a cladding phase.
In one embodiment, the primary phase of the present invention is NaTi 2 (PO 4 ) 3 。
In one embodiment, the stable phase of the present invention includes two of the following: one is M 0.5 Ti 2 (PO 4 ) 3 (m= Sr, ca, mn, mg, co, cu); two are M 1 (TiM 2 )(PO 4 ) 3 ，M 1 ＝Fe、Na、Mn、Sn、Na，M 2 ＝Ge、Nb、Cr、 Sn。
In one embodiment, the content of the stable phase of the present invention is 0.01-1.0%.
In one embodiment, the coating phase of the present invention is added in the form of a liquid phase carbonizable starting material, which after sintering is present in the form of amorphous carbon in an amount of 0-3% and a thickness of 2-100nm.
In one embodiment, in the preparation method of the invention, the key technical points of particle size of the original material, adding sequence of the materials (adding titanium source firstly and adding phosphorus source and sodium source secondly), regulating and controlling pH value of the mixed slurry and the like are key control steps for realizing stable phase and coating phase generation.
Compared with the prior art, the invention has the following advantages:
1. by adding the doped metal ions, a second phase is formed as a stable phase during sintering. The stable phase and the main phase have the same crystal structure, and no lattice distortion is generated; meanwhile, the stable phase has stronger ionic bond force, is uniformly distributed in the main phase, plays a supporting role on the crystal structure of the main phase, and enhances the chemical stability of the main phase. Compared with the prior common doping technology, 3, the stable phase and the main phase form uniform distribution, and the stable support to the crystal lattice is higher
2. Content of stable phase; the proper stable phase content can improve the ionic conductivity of the titanium phosphorus oxide without damaging the crystal structure stability of the sodium titanium phosphate
3. The coating phase is a hydrophilic amorphous carbon material and is formed by carbonizing a liquid-phase carbonized raw material in an inert atmosphere, so that on one hand, the conductivity of the material can be improved, and on the other hand, a stable chemical and electrochemical reaction interface can be provided
4. The liquid phase charrable raw material is water-soluble substance, forms ion level mixing with the coated object, and uniformly covers the surface of the sintered particles after charring; meanwhile, the content of the liquid-phase charrable raw materials is not too high, so that synthesis and growth of crystal grains are not hindered in the sintering process.
The invention uses an ionic resistance and electronic resistance testing method, which comprises the following steps: PFTE is selected as a binder, and the obtained powder is prepared according to the following steps: binder = 90:10, coating the mixture on a Ti foil current collector by adopting a tape casting method, drying and rolling, wherein the loading amount of active substances is 0.3g/cm < 2 >, assembling a symmetrical battery, using 1M sodium sulfate as electrolyte, testing an alternating current impedance Nyquist spectrum (Z 'and Z' in the spectrum are the real part and the imaginary part of impedance under different frequencies), and reading ohmic resistance and ionic resistance.
The invention uses a coating phase content testing method, which comprises the following steps: the test of the coating phase content was performed using differential heat-thermogravimetry.
The invention uses a specific capacity testing method, which comprises the following steps: 10mg of electrode powder is taken, the electrode powder is pressed on a stainless steel mesh with the pressure of 30MPa to serve as a working electrode, a Pt electrode serves as a counter electrode, ag/AgCl serves as a reference electrode, a CV curve of the electrode is tested, the scanning speed is 0.1mv/s, and the specific capacity is calculated according to the peak area.
The invention uses a cyclicity test method, which comprises the following steps: the prepared composite phase/pure phase titanium phosphorus oxide is used as a negative electrode, manganese oxide is used as a positive electrode, stainless steel is used as a current collector, a full battery is assembled, 1M sodium sulfate is used as electrolyte, and the test conditions are accelerated: adjusting pH=10 of electrolyte, testing at 60deg.C with test voltage of 1.0-1.9V
The invention uses an alkali corrosion resistance testing method, which comprises the following steps: the powder obtained by sintering was dissolved in 1M sodium hydroxide solution and magnetically stirred at 80℃for 10 days to test XRD and SEM.
The test results of the invention are as follows:
1. the ionic resistance and electronic resistance of the composite phase titanium phosphorus oxide were reduced by about 30% compared to conventional samples, and the specific capacity was increased by about 10% (see table 1 and fig. 1 below).
2. The cycle stability is greatly improved, and the capacity retention rate of 100 circles is improved from 70% to 80% and 90% under the condition of accelerated test (see figure 2).
3. Meanwhile, corrosion resistance tests show that the composite phase titanium phosphorus oxide still maintains the complete crystal form after being soaked in a strong alkali solution, and the titanium phosphorus oxide obtained by the conventional preparation method in the comparative example is corroded (see figure 3).
Table 1: comparative example composition and test data of examples
The invention may be better understood by reference to the following examples. Those skilled in the art will appreciate that the following examples are provided merely to illustrate the invention and are not intended to limit the scope of the invention. The scope of the invention is defined by the claims that follow.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The following embodiment S1: the main phase raw materials are sodium carbonate, ammonium dihydrogen phosphate and titanium dioxide powder; stable phase raw materials: manganese carbonate, chromium carbonate, monoammonium phosphate. According to the main phase: stationary phase = 99.5: weighing raw materials according to a proportion of 0.5, uniformly dispersing a titanium source in deionized water solution, fully stirring, and then adding sodium source, phosphorus source and stable phase raw materials; according to the following formula with metal ion 8:1, adding sucrose as a coating phase, adjusting the pH value of the slurry to 6.5, and obtaining powder from the obtained slurry by adopting a microwave drying method. And sintering the powder for 10 hours in a nitrogen atmosphere at 700 ℃ to obtain the composite phase titanium phosphorus oxide ceramic powder.
Example S2: the main phase raw materials are sodium dihydrogen phosphate, diammine hydrogen phosphate and titanium hydroxide powder; stable phase raw materials:
magnesium hydroxide, titanium hydroxide, diammonium phosphate. According to the main phase: stationary phase = 99.9:0.1, uniformly dispersing a titanium source in deionized water solution, fully stirring, and then adding a sodium source, a phosphorus source and a stable phase raw material; according to the following formula with metal ion 5:1, adding citric acid as a coating phase, adjusting the pH value of the slurry to 7, and obtaining powder from the obtained slurry by adopting a spray drying method. And sintering the powder for 6 hours in a nitrogen atmosphere at 750 ℃ to obtain the composite phase titanium phosphorus oxide ceramic powder.
Comparative example S3: the main phase raw materials are sodium carbonate, diammine hydrogen phosphate and titanium oxide powder; uniformly dispersing a titanium source in deionized water solution, fully stirring, and then adding a sodium source, a phosphorus source and a stable phase raw material; and (3) regulating the pH value of the slurry to 7.4, and obtaining powder from the obtained slurry by adopting a vacuum drying method. Sintering the powder for 20h in a nitrogen atmosphere at 650 DEG C
And obtaining pure-phase titanium phosphorus oxide ceramic powder.
The patent application refers to the literature or published articles. Cited documents and published articles are incorporated by reference into this application to describe more fully the state of the art to which this invention pertains. It should also be noted that throughout this application, the transitional terms "comprising," "including," or "characterized by" are synonymous, are inclusive or open-ended, and do not exclude additional, unrecited elements or method steps.
Reference to the literature
1.Thermal runaway caused fire and explosion of lithium ion battery,Journal of Power Sources 208(2012)210-224.
2.Lifetime prediction and sizing of lead-acid batteries for microgeneration storage applications, 10.1049/iet-rpg:20080021.
3.Outstanding electrochemical performance of sodium vanadium phosphate cathode co-modified by carbon-coating and titanium-doping for Na-ion batteries,Ceramics International,45(2019)12570-12574。

Claims (11)

1. A titanium phosphorus oxide is composed of a main phase, a stable phase and a coating phase, and is characterized in that the main phase is NaTi x M y (PO 4 ) 3 Wherein m=ti, V or Mn, and x+y=2;
the stable phase is selected from M 0.5 Ti 2 (PO 4 ) 3 And M 1 (TiM 2 )(PO 4 ) 3 Where m= Sr, ca, mn, mg, C or Cu, M 1 = Fe, na, mn, sn or Na, M 2 =ge, nb, cr, or Sn.
2. The titanium phosphorus oxide of claim 1 wherein the stabilizing phase is present in an amount of 0.01 to 1.0%.
3. The titanium phosphorus oxide of claim 1 wherein the coating phase is formed by sintering a liquid phase charrable material selected from the group consisting of polydopamine, resorcinol-formaldehyde resin, glucose, sucrose, fructose, polyvinylpyrrolidone (PVP), tannic acid, citric acid, polyvinyl alcohol, polypyrrole, vitamin C and polyethylene glycol in an amount of no more than 3% and a thickness of 2-100nm.
4. The titanium phosphorus oxide of claim 1 wherein the primary phase is niti 2 (PO 4 ) 3 The stable phase is Mg 0.5 Ti 2 (PO 4 ) 3 Or Mn (TiCr) (PO 4 ) 3 。
5. A method of preparing the titanium phosphorus oxide of claim 1, comprising the steps of: (a) Uniformly dispersing titanium source in water, and then sequentially adding a sodium source and a phosphorus source; (b) adding a stable phase material; (c) adding a coating phase raw material and adjusting the pH value of the slurry to 6-8; (d) obtaining powder from the obtained slurry by a drying method; and (e) sintering the powder to obtain the ceramic powder of the titanium phosphorus oxide.
6. The method of claim 5, wherein the sodium source is selected from the group consisting of sodium phosphate, sodium carbonate, sodium dihydrogen phosphate, sodium hydroxide, and sodium acetate, and has a particle size D50 of less than 3 μm.
7. The method of claim 5, wherein the titanium source is selected from the group consisting of titanium dioxide, titanium hydroxide, metatitanic acid, and tetrabutyl titanate, and has a particle size D50 of less than 1 μm.
8. The method of claim 5, wherein the phosphorus source is selected from the group consisting of phosphoric acid, monoammonium phosphate, diammonium phosphate, ammonium phosphate, sodium dihydrogen phosphate, and disodium hydrogen phosphate, and has a particle size D50 of less than 3 μm.
9. The method of claim 5, wherein the stable phase feedstock is selected from the group consisting of manganese carbonate, chromium carbonate, monoammonium phosphate, magnesium hydroxide, titanium hydroxide, and diammonium phosphate.
10. The method of claim 5, wherein the coating phase is added in a molar ratio of metal ions to the stabilizing phase of 1:1 to 5:1.
11. The method of claim 5, wherein the step (e) sinters the powder at 600-1000 ℃ under an inert atmosphere for 5-20 hours.
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US20160156021A1 (en) * 2014-11-28 2016-06-02 Samsung Electronics Co., Ltd. Positive electrode for lithium ion secondary battery and lithium ion secondary battery including the same
CN106981641A (en) * 2017-05-11 2017-07-25 中南大学 A kind of carbon coating titanium phosphate manganese sodium composite and preparation method thereof and the application in sodium-ion battery
CN106946238A (en) * 2017-05-19 2017-07-14 西南大学 A kind of vanadium phosphate manganese sodium electrode material and its preparation method and application
WO2021253714A1 (en) * 2020-06-15 2021-12-23 宁波锋成先进能源材料研究院有限公司 Carbon/titanium phosphate composite material and preparation method therefor and use thereof

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Title
DONGXUE WANG等: "Intercalation pseudocapacitance in a NASICON-structured Na2CrTi(PO4)3@carbon nanocomposite towards high-rate and long-lifespan sodium-ion-based energy storage", JOURNAL OF MATERIALS CHEMISITRY A, pages 20449 - 20968 *
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