CN108023079B - Mixed transition metal borate anode material and preparation method thereof - Google Patents
Mixed transition metal borate anode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a mixed transition metal borate negative electrode material and a preparation method thereof. The mixed transition metal borate contains two transition metal elements of iron and vanadium, and has FeVBO4Or FeVBO4Chemical formula of/C, wherein FeVBO4Belonging to monoclinic system, cell parametersa=9.4~9.9Å，b=3.0~3.5Å，c=9.1~9.6Å，β=90o~93o，ZAnd = 4. The preparation method comprises the following steps: vanadium salt or vanadium oxide, iron salt or iron oxide, boric acid or boron oxide or borate, citric acid or glucose or other organic carbon materials are used as raw materials, mixed by a sol-gel method, pre-sintered and cured, and finally sintered to obtain the catalyst. The mixed transition metal borate is used as the negative electrode material of the lithium ion battery, and the discharge to lithium voltage platform is about 0.6V (V)vsLi), can effectively avoid the generation of lithium dendrite and improve the safety performance of the lithium ion battery.
Description
Technical Field
The invention belongs to the field of lithium ion battery electrode materials, and particularly relates to a mixed transition metal borate negative electrode material and a preparation method thereof.
Background
With the development of intelligent mobile equipment, electric vehicles and clean energy, the demand of advanced energy storage batteries with high specific energy, good safety and long cycle life is increasingly urgent. Although new battery systems such as lithium-air batteries, lithium-sulfur batteries, aluminum ion batteries, and magnesium ion batteries have been developed in the experimental stage, many problems that are difficult to overcome at present are still faced to commercialization. Nowadays, lithium ion batteries are still mainstream products and best choices in the market of energy storage batteries, and have been successfully and widely applied to the latest fields of various portable electronic products (such as smart phones, tablet computers, notebook computers and the like), unmanned planes, balance cars, electric vehicles, smart grid energy storage and the like. Although the performance of the current lithium ion battery is greatly superior to that of the first generation commercial lithium ion battery more than 20 years ago, the electrochemical composition of the current lithium ion battery still adopts lithium-containing metal oxide as a positive electrode, artificial graphite as a negative electrode and lithium salt organic solution as electrolyte. Through the development of the lithium ion battery for decades, the battery structure is continuously optimized according to the application scene, and indexes such as quick charging, safety performance and energy density are greatly improved. With the increasing maturity of the structural design of the battery, the space for improving the performance of the battery is smaller and smaller, and the key for further improving the performance of the battery is the battery material. The anode material has different choices according to different application requirements: lithium cobaltate for smart phones and tablet computers, lithium iron phosphate or lithium manganate for pure electric buses, and ternary materials for minibuses and passenger cars are trends. In contrast, the selection of the negative electrode material is single, and still is mainly based on graphite carbon materials. Although silicon-based negative electrode materials have been currently used in batteries, they are used in the form of silicon-graphite composite materials due to their large volume expansion during charge and discharge, and the content of silicon is often not more than 10%.
Carbon materials such as hard carbon graphite are common lithium ion battery cathode materials, but the theoretical and actual specific capacities of the carbon materials are low (-300 mAh/g), and the compacted density is small, so that the overall energy density of the cathode is low. In addition, the graphite-based negative electrode material has a low lithium intercalation voltage (<0.1V), lithium precipitation easily occurs to form dendrites, which may pierce the separator to cause internal short circuit; meanwhile, the solid-electrolyte interfacial film (SEI) has poor thermal stability, and the battery can be further decomposed and emit heat in case of overheating. The transition metal oxide type negative electrode material has a high specific capacity but has a high oxidation-reduction potential for lithium metal (ii)>1V) to make the output voltage of the full cellGreatly reduced. In addition to the above two types of negative electrode materials, the use of metal borates as lithium ion negative electrode materials has been gradually coming into the field of view in recent years. Because of the high degree of oxophilicity of boron atoms, metal borate materials have a range of boron-oxygen groups in different oxidation states and in different coordination relationships, e.g., BO3 3-，BO4 5-And BO6 9-And the like. The boron oxygen groups can be further combined with metal ions to form island-shaped, annular, chain-shaped, layered and skeleton-shaped metal borate structures, and various crystal structures bring abundant physicochemical properties to the metal borate. Indeed, the literature reports FeBO3、Fe3BO6、Cr3BO6、VBO3、Co2B2O5、Co3B2O6Electrochemical performance of iso borate compounds in which VBO is used3Discharge of (2) to the lowest lithium potential (-0.4V), Co2B2O5The first discharge specific capacity of (1048 mAh/g) is the highest, and then VBO3（910 mAh/g）。
The invention provides a brand new mixed transition metal borate-FeVBO in a metal borate system, which is never reported by domestic and foreign documents and patents4. The crystal structure of the borate belongs to a monoclinic system, and comprises two transition metal elements of different types and different valence states, namely Fe (+ 2 valence) and V (+ 3 valence), and more importantly, Fe2+Ions and V3+The ion mixture occupies two cation positions in the crystal structure and both appear to have good electrochemical activity. Since the types, valence states and occupation of transition metal elements in the borate are mixed, the borate is called "mixed transition metal borate". The content of Fe element in the earth crust is rich, which is beneficial to reducing the manufacturing cost of the cathode material; the V element can perform multi-electron reaction, and is beneficial to improving the charge-discharge specific capacity of the negative electrode material. Mixed metal borates with lower borate molecular weight and suitable inductionFeVBO4Can output higher capacity under a lower but safe lithium potential, and is a cathode material with application prospect. Based on the technical background, the invention provides FeVBO for the first time4A preparation method of the compound and electrochemical performance of the compound as a lithium ion battery cathode material.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art of the lithium ion battery and further improve the performance of the lithium ion battery cathode material, the invention mainly aims to provide the mixed transition metal borate cathode material which is provided with FeVBO4Of the formula (II) belongs to the monoclinic system, cell parametersa=9.4~9.9 Å，b=3.0~3.5 Å，c= 9.1~9.6 Å，β=90o~93o，ZAnd = 4. The material is very suitable to be used as a novel lithium ion battery cathode material by combining the low cost of the Fe element of the material and the multi-electron reaction of the V element.
Another object of the present invention is to provide the above-mentioned mixed metal borate FeVBO4Compounds and methods for their preparation. The compound is never reported by domestic and foreign documents and patents, and is a brand new compound, so the synthesis method of the compound has great significance.
It is still another object of the present invention to provide a conductive carbon composite material comprising the above mixed transition metal borate compound, which is the above mixed metal borate FeVBO, and a method for preparing the same4The surface of the particles and the space between the particles are coated with conductive carbon, and the chemical composition of the conductive carbon can be expressed as FeVBO4and/C. The addition of conductive carbon can make up the deficiency of the conductivity of the metal borate and reduce FeVBO4Particle size of (b) contributes to FeVBO4The electrochemical performance is fully exerted.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a mixed transition metal borate anode material comprises the following steps:
(1) liquid phase mixing: adding ferric salt or ferric oxide serving as an iron source and vanadium salt or vanadium oxide serving as a vanadium source into water, heating for dissolving, then adding boric acid or boron oxide or borate serving as a boron source, stirring for dissolving, finally adding an organic carbon material serving as a chelating agent, heating for stirring to evaporate redundant moisture, and finally forming high-viscosity jelly (sol); the molar ratio of Fe to V to B in the iron source, the vanadium source and the boron source is 1:1 (0.8-2);
(2) and (3) aging process: heating and aging the sol obtained in the step (1) in an oven at 80-100 ℃ for 12-36 h, and slowly polymerizing colloidal particles to obtain a dry gel precursor mixture;
(3) pre-sintering and curing: placing the precursor mixture obtained in the step (2) in an air atmosphere or an oxygen atmosphere, and firing at 400-600 ℃ for 2-10 h to evaporate crystal water, decompose compounds and completely oxidize carbon into carbon monoxide or carbon dioxide to form a completely cured carbon-free intermediate reaction product;
(4) sintering reaction: grinding the carbon-free intermediate reaction product obtained in the step (3), and sintering the product for 10-40 h at 700-1000 ℃ in a reducing atmosphere to finally obtain the mixed transition metal borate anode material marked as FeVBO4。
The preparation method of the other mixed transition metal borate negative electrode material comprises the following steps:
(1) liquid phase mixing: adding ferric salt or ferric oxide serving as an iron source and vanadium salt or vanadium oxide serving as a vanadium source into water, heating for dissolving, then adding boric acid or boron oxide or borate serving as a boron source, stirring for dissolving, finally adding an organic carbon material serving as a carbon source and a chelating agent, heating and stirring to evaporate redundant moisture, and finally forming high-viscosity jelly (sol); the molar ratio of Fe to V to B in the iron source, the vanadium source and the boron source is 1:1 (0.8-2);
(2) and (3) aging process: placing the sol obtained in the step (1) in an oven at 80-100 ℃ for heating and aging for 12-36 h, and slowly polymerizing colloidal particles to obtain a dry gel precursor mixture;
(3) pre-sintering and curing: placing the precursor mixture obtained in the step (2) in a reducing atmosphere or an inert atmosphere, and firing at 200-400 ℃ for 2-10 h to evaporate crystal water and decompose compounds in the precursor mixture to form a completely cured carbon-containing intermediate reaction product;
(4) sintering reaction: grinding the carbon-containing intermediate reaction product obtained in the step (3), and sintering the product for 10-40 h at 700-1000 ℃ in a reducing atmosphere or an inert atmosphere to finally obtain the mixed transition metal borate anode material marked as FeVBO4/C。
Preferably, the ferric salt in step (1) is selected from ferrous sulfate, ferrous sulfate hydrate, ferric citrate hydrate, ferrous oxalate hydrate, ferric nitrate hydrate, ferrous acetate hydrate, ferric hydroxide or ferric hydroxide hydrate; the iron oxide is selected from ferrous oxide, ferric oxide or ferroferric oxide.
Preferably, the vanadium salt in step (1) is selected from ammonium metavanadate, vanadyl sulfate, vanadyl oxalate, vanadyl acetylacetonate or vanadium acetylacetonate; the oxide of vanadium is selected from vanadium pentoxide, vanadium dioxide or vanadium trioxide.
Preferably, the borate in step (1) is selected from ammonium pentaborate, ammonium pentaborate hydrate, ammonium tetraborate or ammonium tetraborate hydrate.
Preferably, the organic carbon material in the step (1) is more than one of glucose, sucrose, citric acid, cellulose and starch; the adding amount of the organic carbon material is 0.01-50% of the sum of the mass of the iron source, the vanadium source, the boron source and the organic carbon material.
Preferably, the heating and dissolving in the step (1) is to heat to 40-60 ℃ and stir for 20-120 min to dissolve the iron source and the vanadium source; the stirring and dissolving time is 10-30 min; the heating and stirring temperature is 70-90 ℃.
Preferably, the reducing atmosphere is Ar-H2Atmosphere of mixed gas, N2-H2A mixed gas atmosphere, a hydrogen atmosphere or an ammonia atmosphere; the inert atmosphere refers to Ar and N2、CO2Or He atmosphere.
Preferably, the grinding time in the step (4) is 20-60 min.
The mixed transition metal borate negative electrode material is prepared by the preparation method.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the mixed transition metal borate anode material FeVBO4Polyanionic group (BO)4)5-Has a smaller molecular weight than phosphate groups, and combines multiple electron reactions provided by two transition metals (Fe and V) to make FeVBO4The charge-discharge specific capacity of the negative electrode material is higher than that of the traditional lithium ion battery negative electrode materials such as graphite and the like;
(2) the mixed transition metal borate anode material FeVBO4The lithium intercalation potential is slightly higher than that of the currently common graphite negative electrode material, so that the lithium precipitation of the negative electrode caused by voltage polarization during the charging of the full battery can be effectively avoided, and in addition, compared with an oxide negative electrode material, the structure is more stable, oxygen is not easily decomposed, and the safety of the battery can be effectively improved from the aspect of an active material;
(3) the invention is to mixed transition metal borate cathode material FeVBO4Compounding with conductive carbon to obtain the mixed transition metal borate anode material FeVBO4The electrical conductivity and the electrochemical activity of the material are improved, so that the electrochemical performance of the material is fully exerted;
(4) the invention provides a method for synthesizing mixed transition metal borate negative electrode material FeVBO by reducing Fe and V by using a carbon source in an inert atmosphere4The method can avoid or reduce the use of expensive hydrogen as reducing gas, simultaneously avoid the defects of low reaction speed of products and difficult mass production caused by low diffusion rate of hydrogen because the carbon reduction reaction is generated in the raw material, inhibit the excessive growth of particles due to the existence of carbon, reduce the production cost and is suitable for industrialization; (5) the invention synthesizes the mixed transition metal borate anode material FeVBO by using the method of liquid phase mixing and then solid phase sintering4Has the advantages of simple preparation method, uniform mixing of raw materials, convenient operation, low production cost and easy control of the particle size and the shape of the product, and has better industryAnd (5) changing the prospect.
Drawings
FIG. 1 shows the mixed transition metal borate FeVBO synthesized in example 1 (a) and example 2(b)4Powder X-ray diffraction pattern of (A), and its isomorph Fe2BO4Standard X-ray diffraction pattern of (ICSD # 417971);
FIG. 2a is the mixed transition metal borate FeVBO of example 14Scanning Electron Microscope (SEM) images of the powder;
FIG. 2b is the mixed transition metal borate FeVBO of example 34A Scanning Electron Microscope (SEM) image of the/C powder;
FIG. 3 is the mixed transition metal borate FeVBO of example 24(a) And the mixed transition metal borate FeVBO of example 34and/C (b) as a charge-discharge curve diagram of the lithium ion battery negative electrode material.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
The mixed transition metal borate FeVBO of the present example4The preparation method of the cathode material comprises the following specific preparation steps:
(1) liquid phase mixing: 4.986g of iron sulfate (FeSO)4) And 2.985g of vanadium pentoxide (V)2O5) Adding into 200mL deionized water, heating to 40 deg.C, stirring for 20 min to dissolve, adding 2.029g boric acid (H)3BO3) Stirring for 30 min to dissolve, and adding 3.153g citric acid (C)6H8O7) Heating to 70 deg.C as chelating agent, stirring, and evaporating excessive water to form sol;
(2) and (3) aging process: heating and aging the sol obtained in the step (1) in an oven at 80 ℃ for 24 h to obtain a dry gelatinous precursor mixture;
(3) pre-sintering and curing: firing the precursor mixture of the step (2) for 10h at 500 ℃ in an air atmosphere to form a fully cured carbon-free intermediate reaction product;
(4) sintering reaction: grinding the intermediate reaction product of the step (3) for 20 min in Ar-H2Mixed gas atmosphere (95% Ar + 5% H)2) Sintering at 700 ℃ for 40 h to finally obtain the mixed transition metal borate FeVBO4。
The XRD pattern of the final product obtained in this example is shown in a in FIG. 1, and it can be seen from the graph that the mixed transition metal borate FeVBO with higher purity can be obtained by the method4And (3) powder. The Scanning Electron Microscope (SEM) image of the final product obtained in this example is shown in FIG. 2a, and it can be seen from the SEM image that the particle size of the product is about 200-500 nm, and the particle size is not very uniform.
Example 2a mixed transition metal borate of this example, FeVBO4The preparation method of the cathode material comprises the following specific preparation steps:
(1) liquid phase mixing: 5.975 g of ferric citrate and 2.854 g of ammonium metavanadate (NH)4VO3) Adding into 300mL deionized water, heating to 50 deg.C, stirring for 50 min to dissolve, adding 1.171 g ammonium pentaborate (NH)4B5O8) Stirring for 20 min to dissolve, and adding 4.395 g glucose (C)6H12O6) Heating to 80 deg.C as chelating agent, stirring, and evaporating excessive water to form sol;
(2) and (3) aging process: heating and aging the sol obtained in the step (1) in a drying oven at 100 ℃ for 12 h to obtain a dry gel precursor mixture;
(3) pre-sintering and curing: firing the precursor mixture of the step (2) for 2h at 600 ℃ in an air atmosphere to form a fully cured carbon-free intermediate reaction product;
(4) sintering reaction: grinding the intermediate reaction product of the step (3) for 40 min in Ar-H2Mixed gas atmosphere (70% Ar + 30% H)2) Sintering at 850 ℃ for 25 h to finally obtain the mixed transition metal borate FeVBO4。
The XRD pattern of the final product obtained in this example is shown in b of FIG. 1, from which it can be seen that the product has no significant impurities and has a purity higher than that of the product obtained in example 1The purity of the product is higher. The product is used as the negative electrode material of the lithium ion battery, the first charge-discharge curve is shown as the curve a in figure 3, and the discharge voltage platform is about 0.6V (to lithium) ((vsLi), the first discharge specific capacity is about 450mAh/g, and the first charge specific capacity is 280 mAh/g.
Example 3
The carbon composite material FeVBO mixed with the transition metal borate of the embodiment4The preparation method of the/C negative electrode material comprises the following specific preparation steps:
(1) liquid phase mixing: 2.626g of iron oxalate (FeC)2O4) And 6.357g of vanadium acetylacetonate (C)15H21O6V), adding into 250ml deionized water, heating to 60 deg.C, stirring for 120 min to dissolve, adding 1.017g boron oxide (B)2O3) Stirring for 10 min to dissolve, finally adding 6.577g of cane sugar as a carbon source and a chelating agent, heating to 90 ℃, continuously stirring, and evaporating excessive water to finally form sol;
(2) and (3) aging process: heating and aging the sol obtained in the step (1) in a drying oven at 90 ℃ for 36 h to obtain a dry gelatinous precursor mixture;
(3) pre-sintering and curing: putting the precursor mixture obtained in the step (2) in N2-H2Atmosphere of mixed gas (95% N)2+ 5% H2) Firing at 400 ℃ for 6 h to form a completely cured carbon-containing intermediate reaction product;
(4) sintering reaction: grinding the intermediate reaction product in the step (3) for 60min, and performing reaction under N2-H2Atmosphere of mixed gas (95% N)2+ 5% H2) Sintering at 1000 ℃ for 10h to finally obtain the carbon composite material FeVBO of the mixed transition metal borate4/C。
The Scanning Electron Microscope (SEM) image of the final product obtained in this example is shown in FIG. 2b, which shows that the product has a uniform particle size distribution of about 100-200 nm, and is FeVBO, which is a carbon-free product compared with example 14Smaller particle size and more uniform particle size due to inhibition of FeVBO by the presence of carbon4Overgrowth and agglomeration of the particles. The product is used as the negative electrode material of the lithium ion battery and is charged and discharged for the first timeThe curve b in FIG. 3 shows that the initial discharge specific capacity is about 520mAh/g, the initial charge specific capacity is 330mAh/g, and the carbon-free FeVBO product is obtained in comparison with the carbon-free FeVBO product of example 24The specific capacity is higher, because the addition of the conductive carbon can effectively compensate FeVBO4The electrochemical performance of the material is fully exerted due to the insufficient conductivity.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the mixed transition metal borate negative electrode material is characterized by comprising the following steps of:
(1) liquid phase mixing: adding ferric salt or ferric oxide serving as an iron source and vanadium salt or vanadium oxide serving as a vanadium source into water, heating for dissolving, then adding boric acid or boron oxide or borate serving as a boron source, stirring for dissolving, finally adding an organic carbon material serving as a chelating agent, heating and stirring to evaporate redundant moisture, and finally forming sol; the molar ratio of Fe to V to B in the iron source, the vanadium source and the boron source is 1:1 (0.8-2); the organic carbon material is more than one of glucose, sucrose, citric acid, cellulose and starch;
(2) and (3) aging process: heating and aging the sol obtained in the step (1) in an oven at 80-100 ℃ for 12-36 h, and slowly polymerizing colloidal particles to obtain a dry gel precursor mixture;
(3) pre-sintering and curing: placing the precursor mixture obtained in the step (2) in an air atmosphere or an oxygen atmosphere, and firing at 400-600 ℃ for 2-10 h to evaporate crystal water, decompose compounds and completely oxidize carbon into carbon monoxide or carbon dioxide to form a completely cured carbon-free intermediate reaction product;
(4) sintering reaction: grinding the carbon-free intermediate reaction product obtained in the step (3), and sintering the ground carbon-free intermediate reaction product for 10-40 hours at 700-1000 ℃ in a reducing atmosphere to finally obtain the carbon-free intermediate reaction productObtaining the mixed transition metal borate cathode material marked as FeVBO4。
2. The preparation method of the mixed transition metal borate negative electrode material is characterized by comprising the following steps of:
(1) liquid phase mixing: adding ferric salt or ferric oxide serving as an iron source and vanadium salt or vanadium oxide serving as a vanadium source into water, heating for dissolving, then adding boric acid or boron oxide or borate serving as a boron source, stirring for dissolving, finally adding an organic carbon material serving as a carbon source and a chelating agent, heating and stirring to evaporate redundant moisture, and finally forming sol; the molar ratio of Fe to V to B in the iron source, the vanadium source and the boron source is 1:1 (0.8-2); the organic carbon material is more than one of glucose, sucrose, citric acid, cellulose and starch;
(2) and (3) aging process: placing the sol obtained in the step (1) in an oven at 80-100 ℃ for heating and aging for 12-36 h, and slowly polymerizing colloidal particles to obtain a dry gel precursor mixture;
(3) pre-sintering and curing: placing the precursor mixture obtained in the step (2) in a reducing atmosphere or an inert atmosphere, and firing at 200-400 ℃ for 2-10 h to evaporate crystal water and decompose compounds in the precursor mixture to form a completely cured carbon-containing intermediate reaction product;
(4) sintering reaction: grinding the carbon-containing intermediate reaction product obtained in the step (3), and sintering the product for 10-40 h at 700-1000 ℃ in a reducing atmosphere or an inert atmosphere to finally obtain the mixed transition metal borate anode material marked as FeVBO4/C；
The inert atmosphere refers to Ar or He atmosphere.
3. The production method according to claim 1 or 2, wherein the iron salt of step (1) is selected from the group consisting of ferrous sulfate, a hydrate of ferrous sulfate, ferric citrate, a hydrate of ferric citrate, ferrous oxalate, a hydrate of ferrous oxalate, ferric nitrate, a hydrate of ferric nitrate, ferrous acetate, a hydrate of ferrous acetate, ferric hydroxide and a hydrate of ferric hydroxide; the iron oxide is selected from ferrous oxide, ferric oxide or ferroferric oxide.
4. The method according to claim 1 or 2, wherein the vanadium salt of step (1) is selected from ammonium metavanadate, vanadyl sulfate, vanadyl oxalate, vanadyl acetylacetonate or vanadium acetylacetonate; the oxide of vanadium is selected from vanadium pentoxide, vanadium dioxide or vanadium trioxide.
5. The method according to claim 1 or 2, wherein the borate in step (1) is selected from ammonium pentaborate, ammonium pentaborate hydrate, ammonium tetraborate or ammonium tetraborate hydrate.
6. The method according to claim 1 or 2, wherein the organic carbon material in the step (1) is added in an amount of 0.01 to 50% by mass of the sum of the iron source, the vanadium source, the boron source and the organic carbon material.
7. The preparation method according to claim 1 or 2, wherein the heating and dissolving in the step (1) is carried out by heating to 40-60 ℃ and stirring for 20-120 min to dissolve the iron source and the vanadium source; the stirring and dissolving time is 10-30 min; the heating and stirring temperature is 70-90 ℃.
8. The method according to claim 1 or 2, wherein the reducing atmosphere is Ar-H2Atmosphere of mixed gas, N2-H2Mixed gas atmosphere, hydrogen atmosphere or ammonia atmosphere.
9. The method according to claim 1 or 2, wherein the grinding time in step (4) is 20 to 60 min.
10. A mixed transition metal borate anode material prepared by the preparation method of claim 1 or 2.
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