CN105990574A - Coated lithium-rich negative electrode material and preparation method thereof - Google Patents

Coated lithium-rich negative electrode material and preparation method thereof Download PDF

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CN105990574A
CN105990574A CN201510071847.3A CN201510071847A CN105990574A CN 105990574 A CN105990574 A CN 105990574A CN 201510071847 A CN201510071847 A CN 201510071847A CN 105990574 A CN105990574 A CN 105990574A
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王卫涛
刘宇航
周小平
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Weihong Advanced Materials Co
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Microvast Power Systems Huzhou Co Ltd
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Abstract

The invention belongs to the field of lithium ion batteries and relates to a coated lithium-rich negative electrode material which is a metal oxide-coated lithium-rich Li3VO4 negative electrode material and a preparation method thereof. The coated lithium-rich negative electrode material is prepared from base raw materials such as Li3VO4, a lithium source, a coating agent and a dispersant and is a metal oxide-coated lithium-rich Li3VO4 negative electrode material. The coated lithium-rich Li3VO4 negative electrode material has a large capacity, realizes high-rate charge/discharge and has stable cycle performances.

Description

Coated lithium-rich negative electrode material and preparation method thereof
Technical Field
The invention belongs to the field of lithium ion batteries, and relates to a coated lithium-rich negative electrode material, namely lithium-rich Li coated by metal oxide3VO4A negative electrode material and a preparation method thereof.
Background
With the development of new energy fields, the requirements for energy density and power density are higher and higher. Lithium ion batteries, which are currently commonly used in power batteries and emerging electronic devices, have the corresponding advantages of high energy density, high power density and long cycle life, but the most widely commercialized negative active material is a carbon negative material.
Carbon negative electrode materials have more disadvantages: the first charge and discharge may form an SEI film, thereby consuming more electrolyte solution and causing a first efficiency decrease; the potential of the carbon cathode is close to that of lithium, and metal lithium can be separated from the surface of the carbon cathode during heavy current charging and discharging and overcharging to cause the phenomena of short circuit and the like; the carbon cathode is used as an inflammable substance, so that more potential safety hazards exist. And Li of spinel structure4Ti5O12Are becoming the focus of research, but Li4Ti5O12The battery has low relative voltage and poor conductivity (conductivity 10) due to high potential-9S/cm), low energy density, and the like. And Li3VO4Is a lithium vanadium oxide compound with small relative molecular weight, and has larger theoretical capacity when being used as an electrode material of a lithium ion battery>372mAh/g), current research on this material has focused on nanocrystallization and doping. For example, the application of Samsung SDI corporation (CN 101154725A) patent uses one or a mixture of lithium vanadium oxide and vanadium carbide to prepare a negative active material to increase the discharge capacity of the negative active material, but the preparation method requires high temperature of more than 1100 ℃ for preparation, and the Li in the negative active material3VO4Less, with limited indications of its discharge capacity. The patent of the university of three gorges (CN 103474641A) adopts a hydrothermal method to prepare nano Li3VO4The preparation process requires reaction in a hydrothermal kettle for 10-30 hours, and then calcination is carried out in the air at 700 ℃ for 1-10 hours, which wastes time and labor. The patent of the university of three gorges (CN 103496741A) adopts solid phase reaction and high temperature heating to prepare nano Li3VO4However, nano Li3VO4The material is easy to absorb water, so that the cycle performance of the material is poor.
Disclosure of Invention
Based on the above background, the first object of the present invention is to provide a coating having a large capacity, capable of large-rate charge and discharge, and stable cycle performanceType lithium-rich Li3VO4And (3) a negative electrode material. The specific technical scheme is as follows: a coated lithium-rich cathode material is prepared from Li3VO4Lithium source, coating agent and dispersing agent as basic raw materials to prepare the lithium-rich Li coated by the metal oxide3VO4And (3) a negative electrode material.
The cathode material of the invention is made of Li3VO4A lithium source, a dispersant and a coating agent as basic raw materials, wherein Li3VO4The lithium source can be prepared into Li-rich lithium3VO4Then rich in lithium Li3VO4The solid surface is coated with a layer of metal oxide through the combined action of a coating agent and a dispersing agent. The coating layer and Li-rich3VO4The coordination can effectively reduce Li3VO4The water absorption is obtained, and the Li is effectively improved3VO4The metal oxide can effectively isolate the cathode active material from the electrolyte solution, reduce the reaction of the cathode material and the electrolyte solution and improve the stability of the battery.
Preferably, the lithium source includes metallic lithium and a lithium-rich compound. More preferably, the lithium-rich compound is at least one of lithium hydride, lithium hydroxide, lithium carbonate, lithium bicarbonate, lithium oxalate, lithium nitrate, and lithium acetate.
Preferably, the coating agent is B (OR)3、Si(OR)4、Ti(OR)4、Zr(OR)4、Nb(OR)5、Ta(OR)5、Mo(OR)4、W(OR)6、W(OR)5、W(OR)4、Ti(R)4、Zr(R)4、Nb(R)5、Ta(R)5、Mo(R)4、W(R)6、W(R)5And W (R)4At least one of (1); wherein R has the chemical formula CnH2n+1And n is a positive integer. More preferably, the coating agent is tetramethyl silicate, tetraethyl silicate, tetraisopropyl silicate, tetra-n-propyl silicate, tetrabutyl silicate, n-butyl silicate, tetramethyl titanate, tetraethyl titanate, or tetraisopropyl titanateAt least one of propyl ester, tetra-n-propyl titanate, tetrabutyl titanate, n-butyl titanate, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium tetra-n-propoxide, zirconium tetraisobutoxide, zirconium tetra-n-butoxide, niobium penta-methoxide, niobium pentaethoxide, niobium pentapropoxide, molybdenum tetramethoxide, molybdenum tetraethoxyide, molybdenum tetraisopropoxide, molybdenum tetraisobutoxide, molybdenum tetra-n-butoxide, tungsten hexamethoxyxide, tungsten hexaethoxyxide, tungsten hexaisopropoxy-n-propoxide, tungsten hexaisobutoxide, tungsten hexan-butoxide, tungsten tetramethoxide, tungsten tetraethoxyxide, tungsten tetraisopropoxyde, tungsten tetra-n-propoxide, tungsten tetraisobutoxide and tungsten tetra-n-butoxide.
Preferably, the sum of the number of moles of atoms other than carbon atoms, hydrogen atoms and oxygen atoms in the coating agent and the Li3VO4The ratio of the number of moles of vanadium atoms in the alloy is 3:7 to 9: 1. Within the proportion range, a compact coating layer can be obtained, and lithium-rich Li can be effectively prevented3VO4The conductivity of the material is improved while water is absorbed. More preferably, the sum of the number of moles of atoms other than carbon atoms, hydrogen atoms and oxygen atoms in the coating agent and the Li3VO4The ratio of the number of moles of vanadium atoms in the alloy is 3:5 to 7: 1. More preferably, the sum of the number of moles of atoms other than carbon atoms, hydrogen atoms and oxygen atoms in the coating agent and the Li3VO4The ratio of the number of moles of vanadium atoms is 3:4 to 5: 1. The sum of the number of moles of atoms other than carbon, hydrogen and oxygen in the coating agent of the present invention and the Li3VO4The ratio of the number of moles of vanadium atoms in the coating agent is 3:7 to 9:1, which means the sum of the number of moles of metal atoms, B atoms and Si atoms contained in the coating agent and Li3VO4The ratio of the mole number of the medium vanadium atoms to the mole number of the medium vanadium atoms is 3: 7-9: 1. The coating agent and Li are determined according to the contents of metal atoms, B atoms and Si atoms contained in the coating agent when the coating agent is used3VO4The proportion of (A) and (B).
Preferably, the dispersant is at least one of liquid alcohols, ethers, ketones and benzyl alcohol; wherein,the liquid alcohol has the chemical formula CnH2n+1OH and n are positive integers. More preferably, the dispersant is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol, and acetone.
The second purpose of the invention is to provide a preparation method of the coated lithium-rich cathode material, which comprises the following steps: a) li rich in lithium3VO4Preparation: lithium source, Li3VO4Mixing with water, and drying to obtain Li rich in lithium3VO4(ii) a b) Preparing a coated lithium-rich negative electrode material: coating agent, dispersant and lithium-rich Li3VO4Mixing, drying and calcining to obtain Li coated with metal oxide3VO4A lithium rich negative electrode material.
The coating agent adopted by the invention is preferably in molecular level, and a compact coating layer can be formed, thereby achieving more ideal effect.
The preparation method of the invention has simple process and is beneficial to industrial production; and the prepared cathode material has the comprehensive advantages of high capacity, capability of high-rate charge and discharge and stable cycle performance.
Preferably, the lithium source includes lithium atoms and the Li3VO4The molar ratio of (a) to (b) is 1:1 to 10: 1. Further preferably, the lithium source has lithium atoms and the Li3VO4The molar ratio of (A) to (B) is 2: 1-6: 1. As still further preferred, the lithium source has lithium atoms with the Li3VO4The molar ratio of (A) to (B) is 21-4: 1.
Preferably, the calcination temperature in the step b) is controlled to be 500-1000 ℃. More preferably, the calcination temperature in the step b) is controlled to be 600-900 ℃. Preferably, the calcination temperature in step b) is controlled to be 700 to 800 ℃. The shape and the crystal size of the material can be effectively controlled at the temperature of the section, and when the temperature is lower than the temperature section, the material cannot be completely dehydrated; when the temperature is higher than the temperature range, the crystal structure of the material is obviously enlarged, and the performance of the material is reduced. Further, when the coating amount is increased, it is preferable to appropriately decrease the calcination stability and time.
Preferably, the calcination time in the step b) is controlled to be 0.5 to 50 hours. More preferably, the calcination time in step b) is controlled to be 2 to 10 hours. More preferably, the calcination time in step b) is controlled to be 3 to 6 hours.
Preferably, the drying in step a) and step b) is spray drying.
The invention also provides a lithium ion battery anode material, which uses the coated lithium-rich anode material.
A fourth object of the present invention is to provide a lithium ion battery using any of the above-described coated lithium-rich negative electrode materials.
Drawings
FIG. 1 is a battery cycle performance test chart of a battery prepared in example 2 of the present invention;
FIG. 2 is a battery cycle performance test chart of a battery prepared in example 3 of the present invention;
FIG. 3 is a battery cycle performance test chart of a battery prepared in example 4 of the present invention;
fig. 4 is a battery cycle performance test chart of the battery prepared in example 5 of the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
First step synthesis of lithium-rich Li3VO4: 39.2g of V2O5And 75.6g of lithium hydroxide were added to 200.00g of deionized water, followed by sanding to obtain a mixture, the mixture was filtered to obtain a solution, and the solution was spray-driedObtaining Li rich in lithium3VO4。
Second step synthesis of TiO2Coated lithium-rich Li3VO4Lithium ion battery negative electrode material: 19.5g of the above lithium-rich Li were weighed out3VO4(containing Li)3VO414.3g of LiOH 5.2g) was added to absolute ethanol to disperse and sand-grind, and titanium tetraethoxide (50.0g, 34.0 wt% TiO) was added2) And then the sand is ground and then spray-dried. Then calcining the mixture for 40 hours at 500 ℃ to obtain TiO2Coated lithium-rich Li3VO4And (3) a lithium ion battery negative electrode material (abbreviated as LVTO).
Batteries were prepared with the above materials: mixing 0.80g of LVTO material, 0.10g of conductive carbon black and 0.10g of NMP solution (3.3g) containing PVDF to prepare slurry, coating to prepare a pole piece, and selecting a metal lithium piece as a negative pole piece; electrolyte solution selection of LiPF6And optionally an anti-microbial membrane. The first discharge capacity of the battery is 368mAh/g, and the first charge-discharge efficiency is 67.3%. After 50 weeks of circulation, the capacity was maintained at 212mAh/g and the median voltage of discharge was 0.89V.
Example 2:
first step synthesis of lithium-rich Li3VO4: 39.2g of V2O5And 75.6g of lithium hydroxide are added into 200.00g of deionized water, and then sanding treatment is carried out to obtain a mixture, the mixture is filtered to obtain a solution, and the solution is spray-dried to obtain Li rich in lithium3VO4。
Second step synthesis of TiO2Coated lithium-rich Li3VO4Lithium ion battery negative electrode material: 19.5g of the above lithium-rich Li were weighed out3VO4(containing Li)3VO414.3g of LiOH 5.2g) was added to absolute ethanol to disperse and sand-grind, and titanium tetraethoxide (50.0g, 34.0 wt% TiO) was added2) And then the sand is ground and then spray-dried. Then calcining the mixture for 5 hours at the temperature of 600 ℃ to obtain TiO2Coated lithium-rich Li3VO4And (3) a lithium ion battery negative electrode material (abbreviated as LVTO).
Batteries were prepared with the above materials: mixing 0.80g of LVTO material, 0.10g of conductive carbon black and 0.10g of NMP solution (3.3g) containing PVDF to prepare slurry, coating to prepare a pole piece, and selecting a metal lithium piece as a negative pole piece; electrolyte solution selection of LiPF6And optionally an anti-microbial membrane. The test results are shown in fig. 1: the first discharge capacity of the battery is 326mAh/g, and the first charge-discharge efficiency is 84.6%. The capacity is kept at 242mAh/g after 100 cycles, and the median voltage of discharge is 0.93V.
Example 3:
first step synthesis of lithium-rich Li3VO4: will V2O5(39.2g) was added to a clear deionized water (200.00 g deionized water) solution of lithium hydroxide (75.64g) and sanded, the solution was filtered and spray dried to give Li rich lithium3VO4。
Second step synthesis of TiO2Coated lithium-rich Li3VO4Lithium ion battery negative electrode material: 18.0g of the above-mentioned lithium-rich Li were weighed out3VO4(containing Li)3VO413.2g of LiOH 4.8g) was added to absolute ethanol to disperse and sand-grind, and titanium tetraethoxide (10.0g, 34.0 wt% TiO) was added2) And then the sand is ground and then spray-dried. Then calcining the mixture for 1 hour at 900 ℃ to obtain TiO2Coated lithium-rich Li3VO4And (3) a lithium ion battery negative electrode material (abbreviated as LVTO).
Batteries were prepared with the above materials: mixing 0.80g of LVTO material, 0.10g of conductive carbon black and 0.10g of NMP solution (3.3g) containing PVDF to prepare slurry, coating to prepare a pole piece, and selecting a metal lithium piece as a negative pole piece; electrolyte solution selection of LiPF6And optionally an anti-microbial membrane. The test results are shown in fig. 2: the first discharge capacity of the battery is 271mAh/g, and the first charge-discharge efficiency is 79.2%. After 100 weeks of circulation, the capacity was maintained at 227mAh/g, and the median voltage of discharge was 0.91V.
Example 4:
first step synthesis of lithium-rich Li3VO4: 36.4g of V2O5And 50.4g of lithium hydroxide are added into 200.00g of deionized water, then sanding treatment is carried out to obtain a mixture, the mixture is filtered to obtain a solution, and the solution is spray-dried to obtain Li rich in lithium3VO4。
Second step synthesis of TiO2Coated lithium-rich Li3VO4Lithium ion battery negative electrode material: 13.6g of the above-mentioned lithium-rich Li were weighed out3VO4Dispersing in absolute ethanol, sanding, adding tetraethoxytitanium (15.68g, 34% titanium dioxide), sanding again, and spray drying. Then calcining at 550 ℃ for 5h to obtain TiO2Coated lithium-rich Li3VO4And (3) a lithium ion battery negative electrode material (abbreviated as LVTO).
Batteries were prepared with the above materials: mixing 0.80g of LVTO material, 0.10g of conductive carbon black and 0.10g of NMP solution (3.3g) containing PVDF to prepare slurry, coating to prepare a pole piece, and selecting a metal lithium piece as a negative pole piece; electrolyte solution selection of LiPF6And optionally an anti-microbial membrane. The test results are shown in fig. 3: the first discharge capacity of the battery is 490mAh/g, and the first charge-discharge efficiency is 65%. The capacity is maintained at 296mAh/g after the circulation for 100 weeks, and the median voltage of discharge is 0.79V.
Example 5:
first step synthesis of lithium-rich Li3VO4: 36.4g of V2O5And 84.0g of lithium hydroxide are added into 200.00g of deionized water, then sanding treatment is carried out to obtain a mixture, the mixture is filtered to obtain a solution, and the solution is spray-dried to obtain Li rich in lithium3VO4。
Second step of NbO synthesis2Coated lithium-rich Li3VO4Lithium ion battery negative electrode material: the 11.0g of lithium-rich Li was weighed out3VO4(containing Li)3VO46.8g of LiOH and 4.2g of LiOH) are added into absolute ethyl alcohol for dispersion and sanding 1, then niobium n-butyl alcohol (45.45g, containing 99.0 wt% of niobium n-butyl alcohol) is added into the mixture, and then the mixture is sanded and then spray-dried. Then calcining at 650 ℃ for 5h to obtain Nb2O5Coated lithium-rich Li3VO4Lithium ion battery negative electrode material (abbreviated as LNTO).
Batteries were prepared with the above materials: mixing 0.80g of LNTO material, 0.10g of conductive carbon black and 0.10g of NMP solution (3.3g) containing PVDF to prepare slurry, coating to prepare a pole piece, and selecting a metal lithium piece as a negative pole piece; electrolyte solution selection of LiPF6And optionally an anti-microbial membrane. The test results are shown in fig. 4: the first discharge capacity of the battery is 282mAh/g, and the first charge-discharge efficiency is 67%. The capacity is kept for 100 weeks by circulation at 181mAh/g, and the median voltage of discharge is 0.68V.

Claims (23)

1. A coated lithium-rich anode material is characterized in that: the negative electrode material is formed by Li3VO4Lithium source, coating agent and dispersing agent as basic raw materials to prepare the lithium-rich Li coated by the metal oxide3VO4And (3) a negative electrode material.
2. The coated lithium-rich anode material of claim 1, wherein: the lithium source includes metallic lithium and a lithium-rich compound.
3. The coated lithium-rich anode material of claim 2, wherein: the lithium-rich compound is at least one of lithium hydride, lithium hydroxide, lithium carbonate, lithium bicarbonate, lithium oxalate, lithium nitrate and lithium acetate.
4. The coated lithium-rich anode material of claim 1, wherein: the coating agent is B (OR)3、Si(OR)4、Ti(OR)4、Zr(OR)4、Nb(OR)5、Ta(OR)5、Mo(OR)4、W(OR)6、W(OR)5、W(OR)4、Ti(R)4、Zr(R)4、Nb(R)5、Ta(R)5、Mo(R)4、W(R)6、W(R)5And W (R)4At least one of (1); wherein R has the chemical formula CnH2n+1And n is a positive integer.
5. The coated lithium-rich anode material of claim 4, wherein: the coating agent is tetramethyl silicate, tetraethyl silicate, tetraisopropyl silicate, tetra-n-propyl silicate, tetrabutyl silicate, n-butyl silicate, tetramethyl titanate, tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, tetrabutyl titanate, n-butyl titanate, zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium tetra-n-propoxide, zirconium tetraisobutoxide, zirconium tetra-n-butoxide, niobium penta-methoxide and niobium penta-ethoxide, at least one of niobium pentapropoxide, molybdenum tetramethoxide, molybdenum tetraethoxide, molybdenum tetraisopropoxide, molybdenum tetra-n-propoxide, molybdenum tetraisobutoxide, molybdenum tetra-n-butoxide, tungsten hexamethoxylate, tungsten hexaethoxide, tungsten hexaisopropoxide, tungsten hexan-propoxide, tungsten hexaisobutoxide, tungsten hexan-butoxide, tungsten tetramethoxide, tungsten tetraethoxide, tungsten tetraisopropoxide, tungsten tetra-n-propoxide, tungsten tetraisobutoxide and tungsten tetra-n-butoxide.
6. The coated lithium-rich anode material according to claim 4,the method is characterized in that: the sum of the moles of atoms other than carbon, hydrogen and oxygen atoms in the capping agent and the Li3VO4The ratio of the number of moles of vanadium atoms in the alloy is 3:7 to 9: 1.
7. The coated lithium-rich anode material of claim 6, wherein: the sum of the moles of atoms other than carbon, hydrogen and oxygen atoms in the capping agent and the Li3VO4The ratio of the number of moles of vanadium atoms in the alloy is 3:5 to 7: 1.
8. The coated lithium-rich anode material of claim 7, wherein: the sum of the moles of atoms other than carbon, hydrogen and oxygen atoms in the capping agent and the Li3VO4The ratio of the number of moles of vanadium atoms is 3:4 to 5: 1.
9. The coated lithium-rich anode material of claim 1, wherein: the dispersant is at least one of liquid alcohols, ethers, ketones and benzyl alcohol; wherein the liquid alcohol has the chemical formula CnH2n+1OH and n are positive integers.
10. The coated lithium-rich anode material of claim 9, wherein: the dispersant is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol and acetone.
11. The method for preparing the coated lithium-rich anode material according to any one of claims 1 to 10, comprising the following steps:
a) li rich in lithium3VO4Preparation: lithium source, Li3VO4Mixing with water, and drying to obtain Li rich in lithium3VO4；
b) Preparing a coated lithium-rich negative electrode material: coating agent, dispersant and lithium-rich Li3VO4Mixing, drying and calcining to obtain Li coated with metal oxide3VO4A lithium rich negative electrode material.
12. The method for preparing the coated lithium-rich anode material of claim 11, wherein the method comprises the following steps: lithium atoms in the lithium source and the Li3VO4The molar ratio of (a) to (b) is 1:1 to 10: 1.
13. The method for preparing the coated lithium-rich anode material of claim 12, wherein the method comprises the following steps: lithium atoms in the lithium source and the Li3VO4The molar ratio of (A) to (B) is 2: 1-6: 1.
14. The method for preparing the coated lithium-rich anode material of claim 13, wherein the method comprises the following steps: lithium atoms in the lithium source and the Li3VO4The molar ratio of (A) to (B) is 2:1 to 4: 1.
15. The method for preparing the coated lithium-rich anode material of claim 11, wherein the method comprises the following steps: controlling the calcining temperature in the step b) to be 500-1000 ℃.
16. The method for preparing the coated lithium-rich anode material of claim 15, wherein the method comprises the following steps: controlling the calcining temperature in the step b) to be 600-900 ℃.
17. The method for preparing the coated lithium-rich anode material of claim 16, wherein the method comprises the following steps: controlling the calcining temperature in the step b) to be 700-800 ℃.
18. The method for preparing the coated lithium-rich anode material of claim 11, wherein the method comprises the following steps: controlling the calcination time in the step b) to be 0.5-50 hours.
19. The method for preparing the coated lithium-rich anode material of claim 18, wherein the method comprises the following steps: controlling the calcination time in the step b) to be 2-10 hours.
20. The method for preparing the coated lithium-rich anode material of claim 19, wherein the method comprises the following steps: controlling the calcination time in the step b) to be 3-6 hours.
21. The method for preparing the coated lithium-rich anode material of claim 11, wherein the method comprises the following steps: the drying in step a) and step b) is spray drying.
22. A lithium ion battery negative electrode, characterized in that: use of a coated lithium-rich anode material according to any of claims 1 to 10.
23. A lithium ion battery, characterized by: use of a coated lithium-rich anode material according to any of claims 1 to 10.
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