CN111755694A - Titanium phosphate composite material and preparation method and application thereof - Google Patents
Titanium phosphate composite material and preparation method and application thereof Download PDFInfo
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Abstract
The application discloses a titanium phosphate composite material and a preparation method and application thereof, wherein the method comprises the following steps: carrying out dry ball milling I on a lithium source, a titanium source, a phosphorus source and a carbon source to obtain mixed powder I; mixing the mixed powder I with an additive aqueous solution, and drying to obtain a mixed material; carrying out dry ball milling II on the mixed material to obtain mixed powder II; and sintering the mixed powder II to obtain the carbon/titanium phosphate composite material. The method has simple process and easy operation, and simultaneously, the raw materials can be uniformly dispersed during mixing through the dispersion of the additive aqueous solution, the hardness of the material particles after drying can be reduced, and the whole preparation process is green, environment-friendly and pollution-free; when the titanium phosphate composite material prepared by the method is used as a cathode of a water-based lithium ion battery, the specific capacity of the half battery is nearly 88mAh/g, and no obvious attenuation is generated after 100 cycles of circulation.
Description
Technical Field
The application relates to a titanium phosphate composite material and a preparation method and application thereof, belonging to the field of lithium ion batteries.
Background
Organic lithium ion batteries have been widely used in the field of portable power sources and power batteries due to their high open-circuit voltage, high energy density, long cycle life, and low self-discharge rate. However, when the organic lithium ion battery is applied to a megawatt large-scale energy storage system, the use of a large amount of toxic and flammable organic electrolyte greatly reduces the safety of the energy storage system. The solid electrolyte can improve the safety of the battery, but the requirements of large-scale energy storage systems on characteristics such as high power, quick response and the like are difficult to meet. The power performance of the aqueous battery is more excellent. The water-based lithium ion battery integrates the characteristics of an ion-deintercalation type material and a water-based electrolyte, and has the advantages of high safety, good power performance, environmental friendliness and the like. However, the electrochemical stability window of the aqueous lithium ion battery electrolyte is narrow, which greatly limits the operating voltage and energy density of the aqueous lithium ion battery. Meanwhile, the electrochemical reaction environment of the electrode material in the aqueous electrolyte is more complex, side reactions are more, the structure and the electrochemical stability of the material are influenced, and the cycle service life of the battery is limited. These challenges present significant challenges to the development and application of lithium ion battery systems.
Fast ion conductor (NASICON) structured LiTi2(PO4)3Has three-dimensional ion channels and rapid ion conduction capability, and has a plurality of applications in solid electrolytes. However, when used as an electrode material, the low intrinsic electronic conductivity of polyanionic salts limits their electrochemical performance. In addition, the cycle performance of the materials reported earlier is not ideal, and may be related to reasons such as too low lithium intercalation potential (close to the hydrogen evolution potential of the electrolyte, which is likely to cause water decomposition), strong reducibility of the electrode material (reduced state) after ion intercalation (which may cause side reaction with water or dissolved oxygen in water), and poor stability of the electrode/electrolyte interface. But can be prepared by carbon coating, material nanocrystallization, ion doping and other methodsSo as to greatly improve the electrochemical performance. For example, the LiTi with good cycle performance can be prepared by a sol-gel process with tetrabutyl titanate as a titanium source, lithium acetate as a lithium source, phosphoric acid as a phosphorus source and citric acid as a carbon source2(PO4)3And (3) a negative electrode material. However, low-cost LiTi in solid phase and quasi-solid phase using titanium oxide as a titanium source2(PO4)3The preparation process of the cathode material usually adopts a wet ball milling mode to realize the mixing of the raw materials, the problems of the wall hanging of the raw materials, the overflow along with high-temperature gas and the like in the post-treatment process of the method, such as drying, spraying, granulating and the like, not only cause the waste of the materials, but also cause the pollution to the air, and simultaneously, the cycle performance of the obtained materials still has great challenges.
Disclosure of Invention
According to one aspect of the application, the preparation method of the titanium phosphate composite material is simple in process and easy to operate, meanwhile, the raw materials can be uniformly dispersed during mixing through dispersion of the additive aqueous solution, the hardness of material particles after drying can be reduced, post-treatment of the materials is more convenient, post-treatment processes such as spray granulation and the like are avoided, the utilization rate of the raw materials is improved, and the whole preparation process is green, environment-friendly and pollution-free; when the titanium phosphate composite material prepared by the method is used as a cathode of a water-based lithium ion battery, the specific capacity of the half battery is nearly 88mAh/g, and no obvious attenuation is generated after 100 cycles of circulation.
The preparation method of the titanium phosphate composite material is characterized by at least comprising the following steps:
(1) carrying out dry ball milling on a lithium source, a titanium source, a phosphorus source and a carbon source to obtain mixed powder I;
(2) mixing the mixed powder I with an additive aqueous solution, and drying to obtain a mixed material;
(3) crushing the mixed material to obtain mixed powder II;
(4) and sintering the mixed powder II to obtain the carbon/titanium phosphate composite material.
Optionally, the chemical formula of the titanium phosphate in the titanium phosphate composite material is LixTi2(PO4)3Wherein x is 1-1.3.
Optionally, the molar ratio of the lithium source, the titanium source and the phosphorus source in the step (1) is 1-1.3: 2: 3, wherein the lithium source is calculated by the molar amount of lithium element, the titanium source is calculated by the molar amount of titanium element, and the phosphorus source is calculated by the molar amount of phosphorus element;
the mass of the carbon source is 5-25% of the total mass of the lithium source, the titanium source and the phosphorus source.
Optionally, the lithium source is selected from at least one of lithium acetate, lithium carbonate, and lithium hydroxide;
optionally, the titanium source is selected from at least one of titanium dioxide, metatitanic acid, titanium phosphate;
optionally, the phosphorus source is selected from at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate, and phosphoric acid;
optionally, the carbon source is selected from at least one of glucose, sucrose, citric acid.
Optionally, the ball milling in step (1) specifically includes:
the ball milling speed is 200-600 r/min;
the ball milling time is 0.5-5 h;
the ball-to-material ratio is 10-5: 1.
Optionally, the additive in the aqueous additive solution in the step (2) is sodium carboxymethyl cellulose and/or sodium polyacrylate;
the mass concentration of the additive water solution is 1-5%;
the mass ratio of the mixed powder I to the additive aqueous solution is 3-10: 1;
optionally, the mixing in step (2) includes:
under the condition of stirring;
the stirring time is 0.5-5 h.
Optionally, the drying in step (2) includes:
the drying temperature is 70-120 ℃;
the drying time is 5-15 h.
Optionally, the pulverization in the step (3) is selected from dry ball milling or air flow pulverization, wherein the specific conditions of the ball milling comprise:
the ball milling speed is 200-600 r/min;
the ball milling time is 0.5-5 h;
optionally, the particle size of the mixed powder II obtained after the crushing in the step (3) is 20-200 μm.
Optionally, the sintering in step (4) includes:
under an inert atmosphere; wherein the inert atmosphere refers to nitrogen atmosphere or inert atmosphere for seven minutes.
The temperature rising procedure is step-type temperature rising:
firstly preserving heat for 0.5 to 6 hours at 100 to 350 ℃, then preserving heat for 0.5 to 6 hours at 350 to 450 ℃, then preserving heat for 0.5 to 6 hours at 450 to 650 ℃, and finally preserving heat for 2 to 10 hours at 650 to 1000 ℃.
Preferably, the rate of temperature rise is 2 ℃ to 15 ℃/min.
In a specific embodiment, the preparation method comprises the following steps:
step A: the initial raw materials for preparing the titanium phosphate composite material comprise a lithium source, a titanium source, a phosphorus source, a carbon source and other additives. Firstly, weighing a lithium source, a titanium source, a phosphorus source and a carbon source in proportion, then placing the mixture into a ball milling tank for full ball milling, and obtaining a material A (namely mixed powder I) after ball milling and mixing; the feeding molar ratio of the lithium source to the titanium source to the phosphorus source is Li to Ti to P is 1-1.3 to 2: 3, the lithium source is at least one of lithium acetate, lithium carbonate and lithium hydroxide; the titanium source is at least one of titanium dioxide, metatitanic acid and titanium phosphate; the phosphorus source is at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate and phosphoric acid, and the carbon source is at least one of glucose, sucrose and citric acid; the ball milling time is 0.5h to 5h, and the rotating speed is 200r/min to 600 r/min.
Preferably, the raw materials and the dosage are as follows: 7.4g of lithium carbonate, 32.0g of titanium dioxide, 69.0g of ammonium dihydrogen phosphate and 22.0g of sucrose; the ball milling time is 3h, and the rotating speed is 200 r/min.
And B: adding an additive aqueous solution into the material A, stirring uniformly for a long time to fully mix the additive aqueous solution and the material A, and uniformly mixing to obtain a pasty material B; the additive in the additive aqueous solution is at least one of sodium carboxymethylcellulose (CMC) and sodium polyacrylate, the mass fraction of the additive aqueous solution is 1-5%, and the solid-to-liquid ratio of the material is 15-5: 1; the stirring time is 0.5 to 5 hours.
Preferably, the additive used is CMC, the mass of which in aqueous solution is 30g, stirred and ground for 3 h.
And C: and (3) drying the materials in a forced air drying oven, wherein the temperature of the oven is set to be 70-120 ℃, and the time is 5-15 hours, so as to obtain a dried material C.
Preferably, the oven temperature is 100 ℃ for a period of 15 h.
Step D: fully ball-milling the dried material C again to obtain a material D (namely mixed powder II); the ball milling time is 0.5h to 5h, and the rotating speed is 200r/min to 600 r/min.
Preferably, the ball milling time is 3h, and the rotating speed is 200 r/min.
Step E: and (2) sintering the material D in a kiln at high temperature in an inert atmosphere, wherein the inert gas is at least one of argon, nitrogen and helium, the temperature rise procedure is step-type temperature rise, the temperature is kept at 100-350 ℃ for 0.5-6 h, the temperature is kept at 350-450 ℃ for 0.5-6 h, the temperature is kept at 450-650 ℃ for 0.5-6 h, the temperature is kept at 650-1000 ℃ for 2-10 h, the temperature rise speed is 2-15 ℃/min, and the material E is obtained after sintering.
Preferably, the sintering kiln is a tube furnace, the inert gas is argon, the sintering procedure is 300 ℃/3h, 400 ℃/3h, 500 ℃/3h, 800 ℃/8h, and the temperature rise speed is 5 ℃/min.
In a second aspect of the present application, a titanium phosphate composite material prepared by any one of the above preparation methods is provided.
In a third aspect of the application, an application of the titanium phosphate composite material prepared by any one of the preparation methods in the field of water-based lithium ion batteries is provided.
In a fourth aspect of the present application, an electrode is provided, which includes an electrode active material, a conductive agent, a binder and a current collector, wherein the electrode active material is a titanium phosphate composite material prepared by any one of the preparation methods.
Optionally, the conductive agent is selected from at least one of conductive carbon black, ketjen black, or carbon nanotubes.
Optionally, the binder is selected from at least one of polytetrafluoroethylene emulsion, polyvinylidene fluoride, hydroxypropyl cellulose, styrene-butadiene rubber and polyethylene;
the current collector is selected from at least one of a stainless steel net, a stainless steel sheet, a titanium net, a copper net and a porous aluminum foil;
optionally, the active material, the conductive agent and the binder are mixed according to a mass ratio of 7:2: 1;
optionally, the surface density of the electrode active material is 1-2 mg-cm-2。
In a fifth aspect of the present application, a method for preparing the above electrode is provided, which at least comprises the following steps:
and compounding the slurry containing the electrode active material, the conductive agent and the binder on the current collector to prepare the electrode. The electrode active substance is the titanium phosphate composite material prepared by any one of the preparation methods.
Optionally, the conductive agent is selected from at least one of conductive carbon black, ketjen black, or carbon nanotubes.
Optionally, the binder is selected from at least one of polytetrafluoroethylene emulsion, polyvinylidene fluoride, hydroxypropyl cellulose, styrene-butadiene rubber and polyethylene;
the current collector is selected from at least one of a stainless steel net, a stainless steel sheet, a titanium net, a copper net and a porous aluminum foil;
optionally, the active material, the conductive agent and the binder are mixed according to a mass ratio of 7:2: 1;
optionally, the surface density of the electrode active material is 1-2 mg-cm-2。
The compounding includes at least one of coating, rolling, extruding, and kneading.
In a sixth aspect of the present application, there is provided an aqueous lithium ion half-cell comprising:
a negative electrode;
an electrolyte, which is an aqueous solution containing a lithium salt; and
and the positive electrode is at least one of the electrode and the electrode prepared by the preparation method.
Optionally, the negative electrode is an activated carbon cloth.
Further, the water-based lithium ion half-cell also comprises a diaphragm, wherein the diaphragm is selected from at least one of glass fiber filter paper, an AGM diaphragm and a cellulose non-woven fabric diaphragm;
optionally, the lithium salt in the electrolyte is selected from at least one of lithium chlorate, lithium sulfate, lithium nitrate, lithium acetate, lithium formate and lithium phosphate;
optionally, the concentration of lithium ions in the electrolyte is 1.5-2.5M.
In a seventh aspect of the present application, there is provided an aqueous lithium ion full cell comprising:
the negative electrode is at least one of the electrode and the electrode prepared by the preparation method;
an electrolyte, which is an aqueous solution containing a lithium salt; and
a positive electrode containing a positive electrode active material; the positive active material is at least one of lithium manganate, lithium iron phosphate and lithium cobaltate.
Optionally, the lithium salt in the electrolyte is selected from at least one of lithium chlorate, lithium sulfate, lithium nitrate, lithium acetate, lithium formate and lithium phosphate.
Optionally, the electrolyte is a saturated aqueous solution of a lithium salt;
optionally, the aqueous lithium ion full cell further comprises a separator selected from at least one of glass fiber filter paper, an adsorption type glass fiber separator and a cellulose non-woven fabric separator.
The full cell in this application is a secondary cell.
The beneficial effects that this application can produce include:
1) the method is simple and convenient, and easy to operate and produce in batches; in addition, the used materials and equipment are cheap and easy to obtain, and are expected to occupy cost advantage in the subsequent industrial process;
2) firstly, raw material mixture powder is obtained through dry ball milling, then the raw material mixture powder is fully and uniformly dispersed through an additive aqueous solution, and finally the micron-sized reactant powder is obtained through ball milling, and finally the titanium phosphate composite material is obtained through solid-phase sintering, so that the problems of sedimentation, wall hanging and the like of the material after the material is pasty are avoided, the mixture powder is uniformly mixed and dispersed, the utilization rate of the raw material is greatly improved, and the whole preparation process is green, environment-friendly and pollution-free;
3) in a water-based battery, the specific capacity of the full battery assembled by the material prepared by the method can reach 88mAh/g, and the material has no obvious attenuation after 100 cycles of circulation, and is superior to the performance of other titanium phosphate lithium materials synthesized by a solid phase method in the water-based battery.
4) The water system battery completely avoids unsafe factors of organic electrolyte and has a very stable charging and discharging platform.
5) Because the titanium phosphate lithium material has poor conductivity, the carbon-coated titanium phosphate lithium material greatly improves the conductivity.
6) Due to the addition of the additive, the problem of nonuniform mixing caused by the sedimentation of the material after being pasty is solved, and the material is easy to grind after being dried.
Drawings
FIG. 1 is an XRD pattern of a carbon/titanium phosphate composite material provided in example I of the present invention;
FIG. 2 is a scanning electron microscope image of a carbon/titanium phosphate composite material provided in example I of the present invention;
fig. 3 is a diagram showing the charge/discharge specific capacity of the full cell 1 according to the embodiment of the present invention;
fig. 4 is a graph showing the cycle stability of the full cell 1 according to the embodiment of the present invention.
Fig. 5 is a graph of the charge-discharge specific capacity of the full battery provided in the comparative example;
fig. 6 is a graph of full cell cycling stability provided by the comparative example.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
Wherein, sodium carboxymethylcellulose (CMC) is purchased from Jingzhida science and technology limited of Shenzhen, department; the molecular weight is 40 ten thousand with the model number KJGROUP.
EXAMPLE I preparation of carbon/titanium phosphate composite
Step A: firstly, weighing a lithium source, a titanium source, a phosphorus source and a carbon source in proportion, then placing the mixture in a ball milling tank for full ball milling, and obtaining a material A after ball milling and mixing;
wherein the lithium source, the titanium source, the phosphorus source, the carbon source and the dosage are respectively as follows: 7.4g of lithium carbonate, 32.0g of titanium dioxide, 69.0g of ammonium dihydrogen phosphate and 22.0g of sucrose;
the ball milling time is 3h, the rotating speed is 200r/min, and the ball material ratio is 7: 1.
and B: adding an additive aqueous solution into the material A, stirring uniformly for a long time to fully mix the additive aqueous solution and the material A, and uniformly mixing to obtain a pasty material B;
wherein the additive is CMC, the mass concentration of the aqueous solution is 1 percent, the total mass of the aqueous solution is 30g, and the stirring time is 3 h.
And C: and (3) drying the material B in a forced air drying oven to obtain a dried material C.
Wherein the drying time is 15h when the temperature of the oven is 100 ℃.
Step D: fully ball-milling the dried material C again to obtain a material D;
wherein, the ball milling time is 3h, the rotating speed is 200r/min, the ball-material ratio is 7: 1.
step E: sintering the material D in a kiln in an inert atmosphere at a high temperature to obtain a carbon/titanium phosphate composite material;
wherein, the sintering kiln is a tube furnace, the inert gas is argon, the sintering procedure is 300 ℃/3h, 400 ℃/3h, 500 ℃/3h, 800 ℃/8h, and the temperature rise speed is 5 ℃/min.
EXAMPLE II preparation of titanium phosphate @ carbon composites
The procedure is as in example I, except that in step B the additive is sodium polyacrylate.
EXAMPLE III preparation of a carbon/titanium phosphate composite
The same preparation method as that of example I, except that the ball milling process of step D is changed into jet milling, that is, the dried material C is jet milled to obtain the material D (the particle size reaches 20 microns).
Comparative example preparation of carbon/titanium phosphate composite
Adding 7.4g of lithium carbonate, 32.0g of titanium dioxide, 69.0g of ammonium dihydrogen phosphate and 22.0g of sucrose into a mixed solution of water and alcohol (the mass ratio of water to ethanol is 1:10), wherein the mass ratio of the raw material powder to the mixed solution of ethanol and water is 30: 70. ball milling is carried out for 3 hours at a high speed of 200r/min by a ball mill to obtain uniform slurry. And (3) adopting a spray drying method to the obtained slurry, setting the air inlet temperature to be 220 ℃ and the air outlet temperature to be 110 ℃, and collecting the obtained spherical powder precursor. And putting the precursor into a sintering furnace protected by inert gas, wherein the sintering procedure is 300 ℃/3h, 400 ℃/3h, 500 ℃/3h, 800 ℃/8h and the heating speed is 5 ℃/min, thus obtaining the carbon/titanium phosphate composite material.
Example 1 half cell assembly:
half cell structure composition
Electrolyte solution: 2M lithium sulfate (Li)2SO4) Aqueous solution
A diaphragm: glass fiber filter paper (porosity below 1 micron, thickness about 260 micron)
Negative electrode: activated carbon cloth
And (3) positive electrode: the active substance is a carbon/titanium phosphate composite material
The anode preparation process comprises the following steps: adding an active substance, a conductive agent SP and a binder PTFE into an ethanol solution according to the mass ratio of 7:2:1, mixing and stirring to form slurry, coating the slurry on a stainless steel net, and then drying in vacuum. The electrode area is about 1.5cm2The surface density of the active substance is about 1-2 mg cm-2。
The used battery is a CR2032 button battery.
Wherein, the half-cell with the positive active material provided in example i is denoted as half-cell 1; the active material is identified as half cell 2 from the half cell provided in example ii; the half-cell with the active material provided in example iii is denoted half-cell 3; the half cell of the active material provided by the comparative example was designated as half cell a;
example 2 full cell assembly:
full battery structure composition
Electrolyte solution: lithium sulfate (Li)2SO4) Saturated aqueous solution
A diaphragm: glass fiber filter paper (porosity below 1 micron, thickness about 260 micron)
Negative electrode active material: carbon/titanium phosphate composite material
Positive electrode active material: lithium manganate
The negative pole piece manufacturing process comprises the following steps: mixing and stirring an active substance, a conductive agent SP and a binder PTFE in an ethanol solution according to the mass ratio of 7:2:1 to form slurry, coating the slurry on a stainless steel net, and then drying in vacuum. The electrode area is about 1.5cm2The surface density of the active substance is about 1-2 mg cm-2。
The manufacturing process of the positive pole piece comprises the following steps: mixing and stirring an active substance, a conductive agent SP and a binder PTFE in an ethanol solution according to the mass ratio of 8:1:1 to form slurry, coating the slurry on a stainless steel net, and then drying in vacuum. The electrode area is about 1.5cm2The surface density of the active substance is about 1-2 mg cm-2。
The used battery is a CR2032 button battery.
Wherein, the full cell provided by example i for the negative active material is denoted as full cell 1; active material the full cell provided in example ii was designated full cell 2; active material the full cell provided in example iii was designated full cell 3; the full cell provided by the comparative example as the active material was designated as a full cell a.
Example 3 structural characterization of carbon/titanium phosphate composite materials
The carbon/titanium phosphate composite materials provided in examples I to III were tested using an X-ray powder diffractometer, model D8 ADVANCE DAVINC from BRUKER, Germany, and typical test results are shown in FIG. 1. Figure 1 provides materials corresponding to example i. As can be seen from FIG. 1, the main peak positions of the X-ray diffraction spectrum completely correspond to the standard cards one by one, and the carbon/titanium phosphate composite material is proved to be obtained; the diffraction peak has no other impurity peak, which indicates that the purity of the synthesized material is very high, and the purity of the carbon/titanium phosphate composite material is close to 98 percent by calculation.
The carbon/titanium phosphate composite material provided in example i was tested using a field emission scanning electron microscope model Sirion200 from FEI corporation, and typical test results are shown in fig. 2. Figure 2 provides materials corresponding to example i. As shown in FIG. 2, the material has a uniform particle size distribution, with an average particle size of about 20 um;
the materials provided by the embodiments II and III are carbon/titanium phosphate composite materials, and the purity of the carbon/titanium phosphate composite materials is more than 95%, and the particle size of the carbon/titanium phosphate composite materials is 20-200 um.
Example 4 characterization of electrical properties of full cells
The full cells 1 to 3 and a provided in example 1 were subjected to charge/discharge tests and cycle performance tests.
The charge and discharge test conditions include:
measuring a charge-discharge curve of the full cell under a room temperature 1C (100mAh/g) test condition;
measuring the cycle performance of the full cell under the test condition of 1C (100mAh/g) at room temperature to obtain a cycle performance curve;
taking the full cell 1 as a typical representative, as shown in fig. 3, under the test condition, the full cell 1 exerts a specific discharge capacity of about 88mAh/g, and after 100 cycles, the specific discharge capacity is still maintained above 83mAh/g without significant attenuation; the discharge specific capacity of the full batteries 2 and 3 is within the range of 79-85mAh/g, and after 100 times of circulation, the specific capacity is still kept above 71 mAh/g;
as shown in fig. 4, after 100 cycles, the capacity retention rate of the full cell 1 was 94% or more; the discharge capacity retention rates of the full cells 2, 3 were in the range of 83% to 89%.
Referring to fig. 5 and 6, under the same test conditions, the specific discharge capacity of the full battery a provided by the comparative example can only reach 66mAh/g, and the capacity retention rate of the full battery a after 100 cycles is 75%.
Although the present application has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The preparation method of the titanium phosphate composite material is characterized by at least comprising the following steps:
(1) carrying out dry ball milling on a lithium source, a titanium source, a phosphorus source and a carbon source to obtain mixed powder I;
(2) mixing the mixed powder I with an additive aqueous solution, and drying to obtain a mixed material;
(3) crushing the mixed material to obtain mixed powder II;
(4) and sintering the mixed powder II to obtain the carbon/titanium phosphate composite material.
2. The method for preparing the titanium phosphate composite material according to claim 1, wherein the molar ratio of the lithium source to the titanium source to the phosphorus source in the step (1) is 1-1.3: 2: 3, wherein the lithium source is calculated by the molar amount of lithium element, the titanium source is calculated by the molar amount of titanium element, and the phosphorus source is calculated by the molar amount of phosphorus element;
preferably, the mass of the carbon source is 5-25% of the total mass of the lithium source, the titanium source and the phosphorus source;
preferably, the lithium source is selected from at least one of lithium acetate, lithium carbonate and lithium hydroxide;
preferably, the titanium source is selected from at least one of titanium dioxide, metatitanic acid and titanium phosphate;
preferably, the phosphorus source is selected from at least one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate and lithium dihydrogen phosphate;
preferably, the carbon source is selected from at least one of glucose, sucrose, citric acid;
preferably, the ball milling in the step (1) comprises the following specific conditions:
the ball milling speed is 200-600 r/min;
the ball milling time is 0.5-5 h;
the ball-to-material ratio is 10-5: 1.
3. The method for preparing a titanium phosphate composite material according to claim 1, wherein the additive in the aqueous additive solution of step (2) is sodium carboxymethylcellulose and/or sodium polyacrylate;
preferably, the mass concentration of the additive water solution is 1-5%;
preferably, the mass ratio of the mixed powder I to the additive aqueous solution is 3-10: 1;
preferably, the mixing in step (2) includes the following specific conditions:
under the condition of stirring;
the stirring time is 0.5-5 h;
preferably, the drying in step (2) includes the following specific conditions:
the drying temperature is 70-120 ℃;
the drying time is 5-15 h.
4. The method for preparing a titanium phosphate composite material according to claim 1, wherein the pulverization in the step (3) is selected from dry ball milling or jet milling;
preferably, the sintering in step (4) includes:
under an inert atmosphere;
the temperature rising procedure is step-type temperature rising:
firstly preserving heat for 0.5 to 6 hours at 100 to 350 ℃, then preserving heat for 0.5 to 6 hours at 350 to 450 ℃, then preserving heat for 0.5 to 6 hours at 450 to 650 ℃, and finally preserving heat for 2 to 10 hours at 650 to 1000 ℃.
5. The titanium phosphate composite material prepared by the preparation method of any one of claims 1 to 4.
6. The titanium phosphate composite material prepared by the preparation method of any one of claims 1 to 4 is applied to the field of water-based lithium ion batteries.
7. An electrode comprising an electrode active material, a conductive agent, a binder and a current collector, wherein the electrode active material is at least one of the titanium phosphate composite materials prepared by the preparation method of any one of claims 1 to 4.
8. A method of preparing the electrode of claim 7, comprising: and compounding the slurry containing the electrode active material, the conductive agent and the binder on the current collector to prepare the electrode.
9. An aqueous lithium-ion half-cell, comprising:
a negative electrode;
electrolyte solution: the electrolyte is an aqueous solution containing lithium salt;
and (3) positive electrode: the positive electrode is at least one of the electrode provided in claim 7 and the electrode prepared by the preparation method provided in claim 8.
10. An aqueous lithium ion full cell, comprising:
a negative electrode, which is at least one of the electrode provided in claim 7 and the electrode prepared by the preparation method provided in claim 8;
an electrolyte, which is an aqueous solution containing a lithium salt; and
a positive electrode containing a positive electrode active material; the positive active material is at least one of lithium manganate, lithium iron phosphate and lithium cobaltate.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113488647A (en) * | 2021-07-01 | 2021-10-08 | 中国石油大学(华东) | Amorphous SnP containing oxygen vacancies2O7Application of/nitrogen-doped carbon composite material |
| CN113479858A (en) * | 2021-07-01 | 2021-10-08 | 中国石油大学(华东) | Composite material for high-performance alkali metal ion battery cathode |
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| CN113697789A (en) * | 2021-08-27 | 2021-11-26 | 江苏理工学院 | Carbon-coated sodium titanium phosphate composite material and preparation method of negative electrode plate |
| 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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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101330141A (en) * | 2008-07-18 | 2008-12-24 | 清华大学 | Method for preparing lithium ionic battery anode material spherical LiFePO4 /C |
| US20090023069A1 (en) * | 2007-07-20 | 2009-01-22 | Byd Company Limited | Type of Lithium Iron Phosphate Cathode Active Material and Its Method of Synthesis |
| CN101423206A (en) * | 2008-09-27 | 2009-05-06 | 彩虹集团电子股份有限公司 | Method for preparing lithium iron phosphate precursor |
| CN101807696A (en) * | 2010-04-12 | 2010-08-18 | 浙江大学 | Titanium phosphate lithium material used for cathode of lithium ion battery and preparation method thereof |
| CN102468489A (en) * | 2010-11-18 | 2012-05-23 | 芯和能源股份有限公司 | Method for producing lithium iron phosphate material and lithium iron phosphate powder produced thereby |
| CN102745663A (en) * | 2012-07-09 | 2012-10-24 | 四川九驰能源科技股份有限公司 | Method for preparing lithium iron phosphate material |
| CN103165896A (en) * | 2011-12-13 | 2013-06-19 | 湖南省正源储能材料与器件研究所 | Method for preparing lithium iron phosphate/carbon composite material by thickener doping modification |
| CN103956462A (en) * | 2014-04-28 | 2014-07-30 | 张家港智电芳华蓄电研究所有限公司 | Preparation method of lithium iron phosphate-ferrous lithium carbonate composite electrode material |
| CN104934587A (en) * | 2015-04-07 | 2015-09-23 | 黄桂清 | Method for preparing new energy battery active electrode materials by utilizing traditional ilmenite technology |
| CN105047879A (en) * | 2015-07-17 | 2015-11-11 | 河北省科学院能源研究所 | Composite electrode material and preparation method thereof |
| CN105140515A (en) * | 2015-08-27 | 2015-12-09 | 北大先行科技产业有限公司 | Preparation method of lithium ion battery cathode material |
| CN106299267A (en) * | 2015-10-15 | 2017-01-04 | 肖水龙 | A kind of preparation method of titanium phosphate lithium titanate cathode material |
| CN106784702A (en) * | 2016-12-27 | 2017-05-31 | 德清崎辉机械科技有限公司 | A kind of preparation method of high active material |
| CN107068988A (en) * | 2016-12-22 | 2017-08-18 | 山东精工电子科技有限公司 | A kind of preparation method of spherical mesoporous titanium phosphate lithium titanate cathode material |
| CN107359336A (en) * | 2017-07-12 | 2017-11-17 | 北方奥钛纳米技术有限公司 | The preparation method and LiFePO4 and lithium ion battery of LiFePO4 |
| CN108063248A (en) * | 2017-10-29 | 2018-05-22 | 佛山市德方纳米科技有限公司 | Lithium iron phosphate positive material and preparation method thereof and lithium ion battery |
| CN109192936A (en) * | 2018-07-25 | 2019-01-11 | 深圳市德方纳米科技股份有限公司 | A kind of preparation method of LiFePO4 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107732167B (en) * | 2017-09-07 | 2020-08-11 | 浙江瓦力新能源科技有限公司 | Preparation method of sodium titanium phosphate cathode material of water-based ion battery |
| CN107910514A (en) * | 2017-11-06 | 2018-04-13 | 中国人民解放军63971部队 | A kind of preparation method of nitrogen-doped carbon cladding double-core shell titanium phosphate lithium or titanium phosphate sodium |
| KR102663581B1 (en) * | 2018-08-31 | 2024-05-07 | 주식회사 엘지에너지솔루션 | Method for preparing lithium titanium phosphate coated with carbon |
| CN110071277A (en) * | 2019-04-26 | 2019-07-30 | 桑顿新能源科技有限公司 | Si-C composite material and preparation method thereof, battery cathode, battery |
| CN111755694B (en) * | 2020-06-15 | 2022-04-01 | 宁波锋成先进能源材料研究院 | Titanium phosphate composite material and preparation method and application thereof |
-
2020
- 2020-06-15 CN CN202010546618.3A patent/CN111755694B/en active Active
- 2020-11-06 WO PCT/CN2020/127192 patent/WO2021253714A1/en active Application Filing
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090023069A1 (en) * | 2007-07-20 | 2009-01-22 | Byd Company Limited | Type of Lithium Iron Phosphate Cathode Active Material and Its Method of Synthesis |
| CN101330141A (en) * | 2008-07-18 | 2008-12-24 | 清华大学 | Method for preparing lithium ionic battery anode material spherical LiFePO4 /C |
| CN101423206A (en) * | 2008-09-27 | 2009-05-06 | 彩虹集团电子股份有限公司 | Method for preparing lithium iron phosphate precursor |
| CN101807696A (en) * | 2010-04-12 | 2010-08-18 | 浙江大学 | Titanium phosphate lithium material used for cathode of lithium ion battery and preparation method thereof |
| CN102468489A (en) * | 2010-11-18 | 2012-05-23 | 芯和能源股份有限公司 | Method for producing lithium iron phosphate material and lithium iron phosphate powder produced thereby |
| CN103165896A (en) * | 2011-12-13 | 2013-06-19 | 湖南省正源储能材料与器件研究所 | Method for preparing lithium iron phosphate/carbon composite material by thickener doping modification |
| CN102745663A (en) * | 2012-07-09 | 2012-10-24 | 四川九驰能源科技股份有限公司 | Method for preparing lithium iron phosphate material |
| CN103956462A (en) * | 2014-04-28 | 2014-07-30 | 张家港智电芳华蓄电研究所有限公司 | Preparation method of lithium iron phosphate-ferrous lithium carbonate composite electrode material |
| CN104934587A (en) * | 2015-04-07 | 2015-09-23 | 黄桂清 | Method for preparing new energy battery active electrode materials by utilizing traditional ilmenite technology |
| CN105047879A (en) * | 2015-07-17 | 2015-11-11 | 河北省科学院能源研究所 | Composite electrode material and preparation method thereof |
| CN105140515A (en) * | 2015-08-27 | 2015-12-09 | 北大先行科技产业有限公司 | Preparation method of lithium ion battery cathode material |
| CN106299267A (en) * | 2015-10-15 | 2017-01-04 | 肖水龙 | A kind of preparation method of titanium phosphate lithium titanate cathode material |
| CN107068988A (en) * | 2016-12-22 | 2017-08-18 | 山东精工电子科技有限公司 | A kind of preparation method of spherical mesoporous titanium phosphate lithium titanate cathode material |
| CN106784702A (en) * | 2016-12-27 | 2017-05-31 | 德清崎辉机械科技有限公司 | A kind of preparation method of high active material |
| CN107359336A (en) * | 2017-07-12 | 2017-11-17 | 北方奥钛纳米技术有限公司 | The preparation method and LiFePO4 and lithium ion battery of LiFePO4 |
| CN108063248A (en) * | 2017-10-29 | 2018-05-22 | 佛山市德方纳米科技有限公司 | Lithium iron phosphate positive material and preparation method thereof and lithium ion battery |
| CN109192936A (en) * | 2018-07-25 | 2019-01-11 | 深圳市德方纳米科技股份有限公司 | A kind of preparation method of LiFePO4 |
Non-Patent Citations (3)
| Title |
|---|
| 赵玉超等: "Li1.3Al0.3Ti1.7（PO4）3固态电解质的制备及表征", 《电源技术》 * |
| 郑水林 等: "《非金属矿加工技术与应用手册》", 31 May 2005, 冶金工业出版社 * |
| 陈锋: "《表面活性剂、结构、计算与应用》", 31 March 2004, 中国科学技术出版社 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113488647A (en) * | 2021-07-01 | 2021-10-08 | 中国石油大学(华东) | Amorphous SnP containing oxygen vacancies2O7Application of/nitrogen-doped carbon composite material |
| CN113479858A (en) * | 2021-07-01 | 2021-10-08 | 中国石油大学(华东) | Composite material for high-performance alkali metal ion battery cathode |
| CN113479860A (en) * | 2021-07-01 | 2021-10-08 | 中国石油大学(华东) | SbPO4Preparation method of/nitrogen-doped carbon composite material |
| CN113479858B (en) * | 2021-07-01 | 2023-08-11 | 中国石油大学(华东) | Composite material for high-performance alkali metal ion battery cathode |
| CN113479860B (en) * | 2021-07-01 | 2023-08-11 | 中国石油大学(华东) | SbPO (styrene-ethylene-propylene-diene monomer) 4 Preparation method of nitrogen-doped carbon composite material |
| CN113697789A (en) * | 2021-08-27 | 2021-11-26 | 江苏理工学院 | Carbon-coated sodium titanium phosphate composite material and preparation method of negative electrode plate |
| CN114671423A (en) * | 2022-03-25 | 2022-06-28 | 广东马车动力科技有限公司 | Pure-phase titanium phosphate lithium electrolyte and preparation method and application thereof |
| CN116287785A (en) * | 2023-03-24 | 2023-06-23 | 甘肃佰利联化学有限公司 | Method for preparing trivalent titanium by reduction of ferric phosphate-titanium co-production process |
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