CN111082039B - Cuprous oxide doped lithium ion battery cathode material, preparation method and application thereof, and lithium ion battery - Google Patents
Cuprous oxide doped lithium ion battery cathode material, preparation method and application thereof, and lithium ion battery Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a cuprous oxide doped lithium ion battery anode material, a preparation method and application thereof, and a lithium ion battery. The preparation method comprises the following steps: 1) Preparation of La 3+ Doping Cu 2 A core of O; 2) Preparing a lithium-philic layer on the surface of the core obtained in step 1); 3) And 2) preparing a conductive metal layer on the surface of the lithium-philic layer obtained in the step 2), and roasting to obtain the cuprous oxide doped lithium ion battery anode material. The invention is doped with La 3+ Ion coated SiO 2 The lithium-philic layer and the metal silver conductive layer are beneficial to keeping the stability of the Cu-O framework and the chemical stability, conductivity and safety of the material in the process of intercalation and deintercalation of lithium ions, so that the lithium ion battery has longer service life and cycle capacity retention rate.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a cuprous oxide doped lithium ion battery anode material, a preparation method and application thereof, and a lithium ion battery.
Background
Lithium ion batteries have become the most widely used secondary battery in the 21 st century, and in particular, in the last decade, lithium ion batteries have been widely used in the fields of hybrid batteries and pure electric vehicles. The negative electrode material used for the lithium ion battery manufactured by the prior art is mainly a graphite negative electrode, and besides the high capacity and the stable property of the graphite negative electrode material, the low price is one of important factors for the wide application of the graphite negative electrode material. In addition, metal oxides have been widely studied and applied as negative electrode materials for lithium ion batteries, mainly in terms of cost and performance. The main metal oxide comprises CoO, znO, cuO, cu 2 O、FeO、Fe 2 O 3 、TiO 2 、MnO 2 、SnO 2 V (V) 2 O 5 Etc.
The existing negative electrode material mainly has the defects of relatively low initial discharge specific capacity, short cycle life and particularly graphite negative electrode material. The lithium ion battery has the advantages of low capacity and short cycle life, and the most serious is that the volume expansion of the graphite cathode material is serious in the cycle process, so that the cycle discharge capacity and the cycle service life of the lithium ion battery are seriously influenced. The requirements of the existing mobile electrical equipment on the performance of the multi-lithium ion battery are difficult to meet, and particularly, the requirements of the electric automobile on the high capacity, long service life, high multiplying power and high safety of the lithium ion battery are met.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a cuprous oxide doped lithium ion battery anode material, a preparation method and application thereof, and a lithium ion battery. The cuprous oxide doped lithium ion battery cathode material prepared by the technology has good comprehensive electrochemical performance, and can be widely applied to manufacturing of various lithium ion batteries.
The technical scheme provided by the invention is as follows:
a cuprous oxide doped lithium ion battery anode material comprising:
La 3+ doping Cu 2 A core of O;
a lithium-philic layer coated outside the core;
and a conductive metal layer coated outside the lithium-philic layer.
In the technical scheme, the doped cuprous oxide lithium ion battery anode material is doped with La 3+ The ion is favorable for keeping the stability of the Cu-O framework in the process of intercalation and deintercalation of lithium ions, so that the lithium ion battery has longer service life and cycle capacity retention rate (see examples 2 and 4 and figures 7 and 8-11 for details);
specifically, the La 3+ Doping Cu 2 One possible general formula of O is Cu 1-x La x O 1+1.5x ，0.002＜x＜0.008。
Specifically, the lithium-philic layer is SiO 2 Layers, or, siO 2 A mixed layer with silicic acid;
in the technical scheme, the cuprous oxide doped lithium ion battery cathode material is coated with a certain amount of SiO 2 Can effectively improve Li while improving the charge and discharge stability of the anode material + Can significantly improve the specific discharge capacity of the negative electrode active material. The lithium-philic layer is SiO 2 Is favorable for keeping Cu 2 Chemical stability of O core, improving compatibility of anode material particles, electrolyte, adhesive and the like, and being beneficial to improving Li of doped cuprous oxide lithium ion battery anode material + Thereby increasing the electrochemical capacity.
Specifically, the conductive metal layer is an Ag layer.
In the technical scheme, the cuprous oxide doped lithium ion battery anode material is Cu 2 O-coated SiO 2 The outer layer of the coating layer also coatsThe Ag metal coating layer with optimal conductivity can effectively improve the conductivity of the material while improving the charge and discharge stability, the lithium ion intercalation amount and the discharge specific capacity of the anode material, and further can obviously improve the electrochemical performance of the anode active material and the comprehensive electrochemical performance of the manufactured lithium ion battery;
overall, the cuprous oxide doped lithium ion battery anode material is Cu 2 The O metal oxide, the silicon dioxide coating layer and the Ag metal layer have relatively large density, good crystallization stability, good mechanical property, good physical and chemical stability, easy dispersion in aqueous solution when the negative electrode plate is manufactured, better processing performance of the negative electrode plate, effective improvement of compatibility of the negative electrode active material and electrolyte, contribution to improving quality of the electrode plate and performance of the lithium ion battery, and remarkable improvement of production efficiency of the lithium ion battery.
On the other hand, the negative electrode material of the cuprous oxide doped lithium ion battery is Cu 2 O-coated SiO 2 The outer layer of the coating layer also coats the Ag metal coating layer, and meanwhile, because of SiO 2 The Ag has high chemical stability, is difficult to decompose and release oxygen, has good conductivity and electrochemical stability in the electrochemical environment of the lithium ion battery, is respectively positioned on the outer layer and the secondary outer layer of the anode material, and has SiO (silicon oxide) when the silicon oxide can increase the lithium ion intercalation amount, namely the capacity of the battery anode 2 The metal silver coating layer effectively enhances Cu 2 The safety performance of the O anode material or the potential safety hazard of the lithium ion battery possibly caused by anode active substances is greatly eliminated.
On the other hand, compared with the graphite negative electrode material, the doped cuprous oxide lithium ion battery negative electrode material has remarkably higher tap density and higher adhesion or combination performance with the copper foil current collector, so that the phenomena of pole piece powder falling and powder falling are greatly reduced under the condition of properly reducing the using amount of the adhesive, dust pollution to the production environment can be effectively reduced in the manufacturing process of the lithium ion battery negative electrode, and the production efficiency of the lithium ion battery and the product quality of the negative electrode pole piece are remarkably improved, and meanwhile, the environmental efficiency of battery production is also improved.
The invention also provides a preparation method of the cuprous oxide doped lithium ion battery anode material, which comprises the following steps:
1) Preparation of La 3+ Doping Cu 2 A core of O;
2) Preparing a lithium-philic layer on the surface of the core obtained in step 1);
3) And 2) preparing a conductive metal layer on the surface of the lithium-philic layer obtained in the step 2), and roasting to obtain the cuprous oxide doped lithium ion battery anode material.
Based on the technical scheme, the cuprous oxide doped lithium ion battery anode material can be prepared and has the beneficial effects.
Specifically, the step 1) includes the following steps:
1a) Preparing a complex mixture of a cupric salt, a trivalent lanthanum salt and a complexing agent, wherein Cu is contained in the complex mixture 2+ The content of Cu is 0.1-1.0M (mol/L) 2+ With La 3+ The mol ratio of (C) is 100:0.2-100:0.8, cu 2+ The molar ratio of the alkali solution to the complexing agent is 1:0.99-1:1.01, and the alkali solution with the concentration of 0.1-0.5M is added, stirred and mixed uniformly to obtain a mixed solution;
1b) Adding a reducing agent solution with the concentration of 5-15 wt% and an organic acid solution with the concentration of 0.1-0.5M into the mixed solution obtained in the step 1 a), and stirring at the temperature of 45-75 ℃ for reaction to obtain La-containing catalyst 3+ Doping Cu 2 A mixture solution of O;
wherein the volume ratio of the complex mixture, the alkali solution, the reducing agent solution and the organic acid solution is as follows: 50-500:5-30:10-60:5-30.
Specifically, the step 2) includes the following steps:
2a) Adding silicate powder into the mixture solution obtained in the step 1 b), and stirring for dispersion;
2b) Adding hydrochloric acid with the concentration of 0.2-1.0M after the silicate is uniformly dispersed, and continuously stirring for reaction;
2c) Standing for aging after the reaction is finished,centrifuging the mixture after aging to remove solution, eluting the obtained precipitate with 0.01M alkali solution for 3-5 times to obtain La coated with silicic acid 3+ Doping Cu 2 O precipitation;
wherein the volume ratio of the complex mixture to the hydrochloric acid is 50-500:10-50, and the dosage ratio of the silicate powder to the complex mixture is 0.5-7.5 g:50-500/mL based on the amount of the complex mixture in the step 1 a).
Specifically, the step 3) includes the following steps:
3a) La of the coated silicic acid obtained in step 2 c) 3+ Doping Cu 2 Adding O precipitate into silver complex solution with concentration of 0.1-0.25M, sequentially adding reducing agent solution with concentration of 3-10wt% and alkali solution with concentration of 0.1-0.5M, stirring at 45-75deg.C for reaction, centrifuging to obtain precipitate, washing the precipitate with water until pH value of eluate is neutral (pH=6.8-7.2) to obtain Ag-coated SiO 2 Coated La 3+ Doping Cu 2 O；
3b) Coating the Ag-coated SiO obtained in step 3 a) 2 Coated La 3+ Doping Cu 2 Roasting O for 4-12 hours at 180-300 ℃ to obtain the cuprous oxide doped lithium ion battery cathode material;
wherein the volume ratio of the complex mixture, the silver complex solution, the stock solution and the alkali solution is 50-500:10-100:5-30:2-10 based on the amount of the complex mixture in step 1 a).
Specifically, in step 1 a): the cupric salt is selected from any one or a mixture of a plurality of copper nitrate, copper sulfate, copper chloride or copper acetate.
Specifically, in step 1 a): the trivalent lanthanum salt is selected from any one or a mixture of more of lanthanum nitrate, lanthanum sulfate, lanthanum chloride or lanthanum acetate;
specifically, in step 1 a): the complexing agent is selected from any one or more of carboxyethylenediamine, propylenediamine, butylenediamine or pentylene diamine;
specifically, in step 1 a): the alkali is selected from any one or a mixture of a plurality of potassium hydroxide, sodium hydroxide or lithium hydroxide;
specifically, in the step 1 b), the reducing agent is selected from one or more of water chestnut starch, lotus root starch, sweet potato starch or glutinous rice starch, and the selected reducing agent is short-chain polysaccharide (starch) molecules with relatively small molecular weight, is easier to dissolve, hydrolyze and oxidize, and improves reduction of Ag ＋ The efficiency of forming the Ag coating layer;
specifically, in step 2 a), the molecular formula of the silicate is Na 2 SiO 3 ·9H 2 O；
Specifically, in step 3 a): the silver complex is a mixture of silver nitrate and a ligand with the same mole as silver ions, wherein the ligand is selected from any one or more of ethylenediamine, propylenediamine, butylenediamine and pentylene diamine;
specifically, in step 3 a): the alkali is selected from any one or a mixture of a plurality of sodium hydroxide, sodium hydroxide or lithium hydroxide.
Based on the technical scheme, the preparation method of the cuprous oxide doped lithium ion battery anode material has the advantages of relatively simple process technology, simple equipment, high production efficiency, abundant and easily available main raw materials, easy recycling of byproducts, no pollution or low pollution of waste, and good economic benefit and environmental benefit.
Specifically, the preparation method of the cuprous oxide doped lithium ion battery cathode material comprises the following steps:
in the first step, 50-500 mLCu is added 2+ The concentration is 0.1-1.0M (mol/L or below), cu 2+ :La 3+ Copper salt and lanthanum salt with a molar ratio of 100:0.2-100:0.8, and Cu 2+ Adding 5-30 mL of alkali solution with the concentration of 0.1-0.5M into a mixture (hereinafter referred to as a "mixture") solution of the coordination agent complex with the same mole, and uniformly stirring and mixing to obtain a mixed solution;
secondly, adding 10-60 mL of 5-15 wt% reducing agent solution and 5-30 mL of 0.1-0.5M organic acid solution into the mixed solution of the first step, and stirring for 10-45 minutes at 45-75 ℃;
thirdly, adding 0.5 to 7.5g of silicate powder into the mixture solution obtained in the second step, stirring for 3 to 15 minutes, adding 10 to 50mL of hydrochloric acid with the concentration of 0.2 to 1.0M, and continuing stirring for 25 to 55 minutes; standing for 5-25 min, centrifuging the mixture to remove solution, leaching the precipitate with 0.01M alkali solution for 3-5 times to obtain coated silicic acid doped La 3+ Cu of ion 2 Precipitating O cuprous oxide;
fourth, adding the precipitate obtained in the third step into 10-100 mL of silver complex solution with the concentration of 0.1-0.25M, adding 5-30 mL of reducing agent solution with the concentration of 3-10 wt%, adding 2-10 mL of alkali solution with the concentration of 0.1-0.5M, stirring for 10-25 minutes at 45-75 ℃, centrifugally separating, washing the precipitate with water until the pH value of the eluate is neutral (pH=7.0 or about 6.8 or 7.0 or 7.2), and washing the washed silver-coated simple substance and silicon dioxide-coated La 3+ Doping Cu 2 And the O negative electrode material is a modified cuprous oxide lithium ion battery negative electrode material. Roasting the precipitate for 4-12 hours at 180-300 ℃ to obtain the cuprous oxide doped lithium ion battery cathode material.
The invention also provides the cuprous oxide doped lithium ion battery anode material prepared by the preparation method of the cuprous oxide doped lithium ion battery anode material.
The cuprous oxide doped lithium ion battery cathode material provided by the technical scheme has wide particle size distribution, the particle size range is 100 nm-2.5 mu m, the particle size mainly depends on the doping ion content, the silicon dioxide and metal Ag coating amount and specific preparation process parameters of the material, the doping ion amount, the silicon dioxide and metal Ag coating amount and the coating thickness are easy to control, and the prepared doping Cu is easy to control 2 Particle size of O negative electrode material (see examples 1-4, figures 1-4 of the specification);
the cuprous oxide doped lithium ion battery anode material provided by the technical scheme is polyhedral particles with larger specific surface area, is beneficial to contact compatibility of active substances and electrolyte, and improves the electrolyteThe wetting efficiency of the electrode and the lithium ion battery is improved, the polyhedron shape is favorable for the full contact of the anode material with the conductive agent, the adhesive, the solvent and the like, the production efficiency of anode slurry is favorable for improving, and Cu is further improved 2 Electrochemical performance of O active material the electrochemical performance of the electrochemical performance grade cell is integrated (see examples 3-4, figures 3-4 of the description for details).
La of doped cuprous oxide lithium ion battery anode material provided by the technical scheme 3+ The doping amount, the particle size of the silicon dioxide, the thickness, the content and the like of the silicon dioxide and the metal Ag coating layer are easy to control, and La can be prepared according to the requirements of different types of lithium ion batteries (multiplying power type lithium ion batteries, capacity type lithium ion batteries and the like) 3+ Cu with certain difference in doping amount, coating amount of silicon dioxide and metal Ag, particle size and comprehensive electrochemical performance 2 And O negative electrode material.
The invention also provides application of the cuprous oxide doped lithium ion battery cathode material as a lithium ion battery cathode material.
Based on the technical scheme, the lithium ion battery manufactured by adopting the cuprous oxide doped lithium ion battery anode material provided by the invention has higher charge-discharge specific capacity and high-rate discharge effect, and Cu 2 The highest first discharge specific capacity of the O anode material reaches 668mAh/g (see example 2 for details), and the highest first discharge specific capacity of the commercial graphite is 348mAh/g (the theoretical capacity of the graphite is 370mAh/g for details, see figure 8); the 1C multiplying power is 1000 times, the capacity retention rate of charge and discharge cycles is not lower than 90% (see AB in examples 2 and 4 and fig. 7 for details), and the capacity retention rate of 665 times of the comparative sample is 69.5% (see C in fig. 7 for details); 1180 charge-discharge cycles have a discharge efficiency of 93.77% and 90.8% (see AB in example 2,4, fig. 8 for details), whereas 786 cycles of the comparative sample are only 73.54% (see C in fig. 8 for details).
The invention also provides a lithium ion battery, which comprises a battery cathode, wherein the material of the battery cathode comprises the lithium ion battery cathode material provided by the invention.
Correspondingly, the positive electrode material can be lithium cobaltate, lithium manganate or lithium nickel cobalt manganate (ternary) positive electrode material, the capacity of the formed battery can reach 99% of the design capacity, the nominal voltage can reach more than 3.7V, and the requirement of single-cell voltage is met.
Drawings
FIG. 1 shows a Cu-doped alloy prepared in example 1 2 SEM (scanning electron microscope) pictures of negative electrode materials of O lithium ion batteries;
FIG. 2 is a Cu-doped alloy prepared in example 2 2 SEM (scanning electron microscope) pictures of negative electrode materials of O lithium ion batteries;
FIG. 3 is a Cu-doped alloy prepared in example 2 2 XRD curve of negative electrode material of O lithium ion battery;
FIG. 4 shows a Cu-doped alloy prepared in example 3 2 SEM (scanning electron microscope) pictures of negative electrode materials of O lithium ion batteries;
FIG. 5 is a Cu-doped alloy prepared in example 4 2 SEM (scanning electron microscope) pictures of negative electrode materials of O lithium ion batteries;
FIG. 6 is a Cu-doped alloy prepared in example 4 2 XRD curve of negative electrode material of O lithium ion battery;
FIG. 7 shows a Cu-doped alloy prepared in example 2 2 The charge-discharge capacity of the O anode material;
FIG. 8 shows a Cu-doped alloy prepared in example 4 2 And the charge-discharge cycle discharge efficiency of the O anode material.
Wherein: in fig. 7 and 8, A, B is the sample prepared in examples 2 and 4, respectively, and C is the comparative graphite sample.
FIG. 9 shows a Cu-doped alloy prepared in example 1 2 Initial charge-discharge performance graph of the battery was measured at 1C magnification of the O negative electrode material.
FIG. 10 shows a Cu-doped alloy prepared in example 1 2 And measuring the cycle performance diagram of the battery by 2C multiplying power of the O anode material.
FIG. 11 shows a Cu-doped alloy prepared in example 1 2 And measuring the high-rate cycle performance diagram of the battery by 5C rate of the O anode material.
Detailed Description
The principles and features of the present invention are described below with examples only to illustrate the present invention and not to limit the scope of the present invention.
Example 1
Doping cladding doping Cu 2 The preparation method of the O anode material comprises the following steps:
first, 50mLCu is obtained 2+ The concentration is 0.1M, cu 2+ :La 3+ Adding 5mL of 0.1M potassium hydroxide solution into a mixed solution of copper nitric acid and lanthanum nitrate with the molar ratio of 100:0.2 and containing 5 millimoles (about 0.34 g) of ethylenediamine, and stirring and mixing uniformly;
secondly, adding 10mL of water chestnut starch reducing agent solution with the concentration of 5wt% and 5mL of acetic acid solution with the concentration of 0.1M into the mixed solution, and stirring and reacting for 45 minutes at the temperature of 45 ℃ to obtain a mixture solution;
thirdly, adding 0.5g of sodium silicate powder into the mixture solution obtained in the second step, stirring for 3 minutes, adding 10mL of hydrochloric acid with the concentration of 0.2M, and continuing stirring for 25 minutes; standing for 5 min, centrifuging the mixture to remove the solution, leaching the precipitate with 0.01M potassium hydroxide solution for 3-5 times to obtain coated silicic acid doped La 3+ Cu of (2) 2 O precipitation;
fourthly, adding the precipitate obtained in the third step into 10mL of silver complex solution with the concentration of 0.1M, adding 5mL of water chestnut starch reducing agent solution with the concentration of 3wt%, adding 2mL of 0.1M potassium hydroxide solution, stirring and reacting for 10 minutes at the temperature of 75 ℃, centrifugally separating, washing the precipitate with water until the pH value of an eluate is neutral, and roasting the washed precipitate for 12 hours at the temperature of 180 ℃ to obtain the La coated with silicon dioxide with a simple substance coated with silver on the surface 3+ Doping Cu 2 O anode material, i.e. Cu doped 2 And O negative electrode material.
The morphology, the particle size, the atomic ratio and the crystal structure of the synthesized modified cuprous oxide cathode material are respectively measured by SEM, EDS, XRD and other technologies, and the obtained doped Cu 2 The O anode material is mainly polyhedral particles with the particle size range of about 0.1-1.5 μm and the average particle size of about 0.65 μm (shown in figure 1), la 3+ The doping amount (Cu: la atomic ratio) was about 1000:1.81, and the silica coating amount (Cu: si atomic ratio) was about 100:23.7; the coating amount of Ag (Cu: ag atomic ratio) is about 100:12.9, and the synthesized doped Cu 2 O is a cubic face-centered crystal; under the condition of 1C multiplying power, the initial discharge specific capacity of the cuprous oxide anode active material is 651mAh/g, and specific electrical property tests are shown in example 5 and figures 9-11.
Example 2
Doping cladding doping Cu 2 The preparation method of the O anode material comprises the following steps:
first, 100mLCu is obtained 2+ The concentration is 0.3M, cu 2+ :La 3+ Adding 10mL of 0.2M sodium hydroxide solution into a compound mixture solution containing copper sulfate and lanthanum sulfate in a molar ratio of 100:0.4 and 30 mM propylene diamine, and uniformly stirring and mixing;
secondly, adding 10mL of 8wt% lotus root starch reducing agent solution into the mixed solution, adding 10mL of 1.0M propionic acid solution, and stirring for 35 minutes at 55 ℃;
thirdly, adding 1.5g of sodium silicate powder into the mixture solution obtained in the second step, stirring for 6 minutes, adding 15mL of 0.4M hydrochloric acid, and continuing stirring for 35 minutes; standing for 10 min, centrifuging the mixture to remove solution, leaching the precipitate with 0.01M sodium hydroxide solution for 3-5 times to obtain coated silicic acid doped La 3+ Cu of ion 2 O precipitation;
fourthly, adding the precipitate obtained in the third step into 30mL of 0.12M silver complex solution, adding 10mL of lotus root starch solution with the concentration of 5wt%, stirring for 15 minutes at 65 ℃, centrifugally separating, washing the precipitate with water until the pH value of an eluate is neutral, and roasting the washed precipitate at 220 ℃ for 8 hours to obtain the surface silver-coated simple substance, namely the silicon dioxide-coated La 3+ Doping Cu 2 O anode material, i.e. Cu doped 2 And O negative electrode material.
The morphology, the particle size, the atomic ratio and the crystal structure of the synthesized modified cuprous oxide cathode material are respectively measured by SEM, EDS and XRD, and the obtained doped Cu 2 The O anode material is mainly polyhedral particles with particle size of about 0.2-2.0 μm, average particle size of about 1.0 μm (shown in figure 2), la 3+ DopingThe amount (Cu: la atomic ratio) was about 1000:3.53, and the silica coating amount (Cu: si atomic ratio) was about 100:13.3; the coating amount of Ag (Cu: ag atomic ratio) is about 100:10.4, and the synthesized doped Cu 2 O is cubic face centered crystal (see figure 3 for details); under the condition of 1C multiplying power, the initial discharge specific capacity of the cuprous oxide anode active material is 668mAh/g, the capacity retention rate of 1000 charge-discharge cycles is 91.8% (see A in figure 7 for details), and the capacity retention rate of a comparative sample 665 charge-discharge cycles is 69.5% (see C in figure 7 for details); 1180 charge-discharge cycles have a discharge rate of 93.77% (see FIG. 8 for details A), and the 786 cycle efficiency of the comparative sample is 73.54% (see FIG. 8 for details C).
Example 3
Doping cladding doping Cu 2 The preparation method of the O anode material comprises the following steps:
first step, 200mLCu 2+ The concentration is 0.75 to 0.75M, cu 2+ :La 3+ Adding 20mL of lithium hydroxide solution with the concentration of 0.3M into a mixed solution of copper chloride and lanthanum chloride with the molar ratio of 100:0.6 and containing 0.15 mol of butanediammonium, and stirring and mixing uniformly;
secondly, adding 40mL of sweet potato starch solution with the concentration of 12wt% into the mixed solution, adding 20mL of butyric acid solution with the concentration of 0.3M, and stirring for 25 minutes at the temperature of 65 ℃;
thirdly, adding 4.0g of sodium silicate powder into the mixture solution obtained in the second step, stirring for 12 minutes, adding 30mL of hydrochloric acid with the concentration of 0.8M, and continuing stirring for 45 minutes; standing for 20 min, centrifuging the mixture to remove the solution, leaching the precipitate with 0.01M lithium hydroxide solution for 3-5 times to obtain coated silicic acid doped La 3+ Cu of ion 2 O precipitation;
fourth, adding the precipitate obtained in the third step into 60mL of silver complex solution with the concentration of 0.2M, adding 20mL of sweet potato starch reducing agent solution with the concentration of 8wt%, stirring for 20 minutes at 55 ℃, centrifugally separating, washing the precipitate with water until the pH value of an eluate is neutral, and roasting the washed precipitate at 260 ℃ for 6 hours to obtain the La with the surface coated with silver simple substance and silicon dioxide 3+ Doping Cu 2 O anode material, i.e. Cu doped 2 And O negative electrode material.
The morphology, the particle size, the atomic ratio and the crystal structure of the synthesized modified cuprous oxide cathode material are respectively measured by SEM, EDS and XRD, and the obtained doped Cu 2 The O anode material is mainly polyhedral particles with the particle size range of about 0.25-2.0 μm and the average particle size of about 1.25 μm (see figure 4 for details), la 3+ The doping amount (Cu: la atomic ratio) is about 1000:5.26, and the silicon dioxide coating amount (Cu: si atomic ratio) is about 100:9.3; the coating amount of Ag (Cu: ag atomic ratio) is about 100:6.8, and the synthesized doped Cu 2 O is a cubic face-centered crystal. The initial specific discharge capacity of the cuprous oxide negative electrode active material is 625mAh/g under the condition of 1C multiplying power.
Example 4
Doping cladding doping Cu 2 The preparation method of the O anode material comprises the following steps:
first, 500mLCu is obtained 2+ At a concentration of 1.0. 1.0M, cu 2+ :La 3+ Adding 30mL of sodium hydroxide solution with the concentration of 0.5M into a compound mixture solution containing 0.5 mol of pentanediamine and copper acetate and lanthanum acetate with the mol ratio of 100:0.8, and stirring and mixing uniformly;
secondly, adding 60mL of glutinous rice starch solution with the concentration of 15wt% and 30mL of succinic acid solution with the concentration of 0.5M into the mixed solution, and stirring for 10 minutes at the temperature of 75 ℃;
thirdly, adding 7.5g of sodium silicate powder into the mixture solution obtained in the second step, stirring for 15 minutes, adding 50mL of hydrochloric acid with the concentration of 1.0M, and continuing stirring for 55 minutes; standing for 25 min, centrifuging the mixture to remove solution, eluting the precipitate with 0.01M sodium hydroxide solution for 3-5 times to obtain coated silicic acid doped La 3+ Cu of ion 2 O precipitation;
fourth, adding the precipitate obtained in the third step into 250mL of 0.05M silver complex solution, adding 300mL of 10wt% reducing agent solution, stirring for 5 minutes at 50 ℃, centrifugally separating, washing the precipitate with water until the pH value of an eluate is neutral, and roasting the washed precipitate at 300 ℃ for 4 hours to obtain the surface silver coated sheetCoating La with silica 3+ Doping Cu 2 O anode material, i.e. Cu doped 2 And O negative electrode material.
The morphology, the particle size, the atomic ratio and the crystal structure of the synthesized modified cuprous oxide cathode material are respectively measured by SEM, EDS and XRD, and the obtained doped Cu 2 The O anode material is mainly polyhedral particles with particle size of about 0.5-2.5 μm and average particle size of about 1.5 μm (shown in figure 5), la 3+ The doping amount (Cu: la atomic ratio) is about 1000:7.3, and the silicon dioxide coating amount (Cu: si atomic ratio) is about 100:4.1; the coating amount of Ag (Cu: ag atomic ratio) is about 100:3.6, and the synthesized doped Cu 2 O is cubic face centered crystal (see FIG. 6 for details). Under the condition of 1C multiplying power, the initial discharge specific capacity of the cuprous oxide anode active material is 649mAh/g, the capacity retention rate of 1000 charge-discharge cycles is 90.8% (see B in figure 7 in detail), the capacity retention rate of a comparative sample for 665 charge-discharge cycles is 69.5% (see C in figure 7 in detail), the charge-discharge efficiency of 1180 cycles is 90.8% (see B in figure 8 in detail), and the charge-discharge efficiency of a comparative sample for 786 cycles is 73.54% (see C in figure 8 in detail).
Example 5
The cuprous oxide negative electrode active material synthesized in example 1 of the present invention was as follows: conductive agent (acetylene black): the mass ratio of the adhesive (SBR) is 93-96:2.5-4.5:1.5-2.5, a negative electrode is manufactured, the positive electrode active material is a lithium nickel manganese oxide ternary material (designed according to the positive electrode capacity surplus coefficient of 1.15, namely the positive electrode design formula capacity is larger than the negative electrode formula capacity of 15%), the manufactured 112535 soft package lithium ion test battery with 1000mAh capacity is subjected to initial charge and discharge performance measurement by 1C multiplying power under the conditions of 4.2V of charge limiting voltage and 3.0V of discharge cut-off voltage, the cycle performance of the battery is measured by 2C multiplying power, and the high multiplying power cycle performance of the battery is measured by 5C multiplying power. The test open circuit voltage and the internal resistance are respectively in the ranges of 3.82-3.915V and 11.34-26.45 mΩ. The specific capacity of the first charge and discharge of the test battery 1C is 651mAh/g, the 891 th cycle discharge efficiency is more than 99%, the 2557 th cycle discharge efficiency is more than 90% (2558 cycle discharge efficiency is 89.88%), and the 1C multiplying power cycle life (calculated by the discharge efficiency being less than 75%) exceeds 2558 cycles (see figure 9 for details); test battery 2C rate charge-discharge cycle efficiency: 570 th cycle discharge efficiency is greater than 99%, 1280 th cycle discharge efficiency is greater than 95%, 2011 th cycle discharge efficiency is greater than 90% (2012 cycle discharge efficiency is 89.92%), and 2C rate cycle life (discharge efficiency is less than 75% calculated) exceeds 2012 cycles (see figure 10 for details); test battery 5C rate charge-discharge cycle efficiency: the 330 th cycle discharge efficiency is more than 95%, the 1050 th cycle discharge efficiency is more than 90%, the 1652 cycle discharge efficiency is more than 80% (1653 cycle discharge efficiency is 79.96%), and the 5C multiplying power cycle life (calculated by the discharge efficiency being less than 75%) exceeds 1653 cycles (see figure 11 for details).
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (9)
1. The cuprous oxide doped lithium ion battery cathode material is characterized by comprising the following components:
La 3+ doping Cu 2 A core of O;
a lithium-philic layer coated outside the core, the lithium-philic layer being SiO 2 Layers, or, siO 2 A mixed layer with silicic acid;
and a conductive metal layer coated outside the lithium-philic layer, wherein the conductive metal layer is an Ag layer.
2. The preparation method of the cuprous oxide doped lithium ion battery cathode material is characterized by comprising the following steps of:
1) Preparation of La 3+ Doping Cu 2 A core of O;
2) Preparing a lithium-philic layer on the surface of the core obtained in the step 1), wherein the lithium-philic layer is SiO 2 Layers, or, siO 2 A mixed layer with silicic acid;
3) And 2) preparing a conductive metal layer on the surface of the lithium-philic layer obtained in the step 2), and roasting to obtain the cuprous oxide doped lithium ion battery anode material, wherein the conductive metal layer is an Ag layer.
3. The method for preparing the negative electrode material of the cuprous oxide doped lithium ion battery according to claim 2, wherein the step 1) comprises the following steps:
1a) Preparing a complex mixture of a cupric salt, a trivalent lanthanum salt and a complexing agent, wherein Cu is contained in the complex mixture 2+ The content of Cu is 0.1-1.0M 2+ With La 3+ The mol ratio of (C) is 100:0.2-100:0.8, cu 2+ The molar ratio of the alkali solution to the complexing agent is 1:0.99-1:1.01, and the alkali solution with the concentration of 0.1-0.5M is added, stirred and mixed uniformly to obtain a mixed solution;
1b) Adding a reducing agent solution with the concentration of 5-15 wt% and an organic acid solution with the concentration of 0.1-0.5M into the mixed solution obtained in the step 1 a), and stirring at the temperature of 45-75 ℃ for reaction to obtain La-containing catalyst 3+ Doping Cu 2 A mixture solution of O;
wherein the volume ratio of the complex mixture, the alkali solution, the reducing agent solution and the organic acid solution is as follows: 50-500:5-30:10-60:5-30.
4. A method for preparing a negative electrode material of a doped cuprous oxide lithium ion battery as claimed in claim 3 wherein said step 2) comprises the steps of:
2a) Adding silicate powder into the mixture solution obtained in the step 1 b), and stirring for dispersion;
2b) Adding hydrochloric acid with the concentration of 0.2-1.0M after the silicate is uniformly dispersed, and continuously stirring for reaction;
2c) Standing for aging after the reaction is completed, centrifuging the mixture to remove solution after the aging is completed, leaching the obtained precipitate with 0.01M alkali solution for several times to obtain La coated with silicic acid 3+ Doping Cu 2 O precipitation;
wherein the volume ratio of the complex mixture to the hydrochloric acid is 50-500:10-50, and the dosage ratio of the silicate powder to the complex mixture is 0.5-7.5 g:50-500 mL based on the amount of the complex mixture in the step 1 a).
5. A method for preparing a negative electrode material of a doped cuprous oxide lithium ion battery as claimed in claim 4 wherein said step 3) comprises the steps of:
3a) La of the coated silicic acid obtained in step 2 c) 3+ Doping Cu 2 Adding O precipitate into silver complex solution with concentration of 0.1-0.25M, sequentially adding reducing agent solution with concentration of 3-10wt% and alkali solution with concentration of 0.1-0.5M, stirring at 45-75deg.C for reaction, centrifuging to obtain precipitate, washing the precipitate with water until pH value of eluate is neutral, and obtaining Ag coated SiO 2 Coated La 3+ Doping Cu 2 O；
3b) Coating the Ag-coated SiO obtained in step 3 a) 2 Coated La 3+ Doping Cu 2 Roasting O for 4-12 hours at 180-300 ℃ to obtain the cuprous oxide doped lithium ion battery cathode material;
wherein the volume ratio of the complex mixture, the silver complex solution, the stock solution and the alkali solution is 50-500:10-100:5-30:2-10 based on the amount of the complex mixture in step 1 a).
6. The method for preparing the cuprous oxide doped lithium ion battery anode material according to claim 5, wherein the method comprises the following steps:
in step 1 a):
the cupric salt is selected from any one or a mixture of a plurality of copper nitrate, copper sulfate, copper chloride or copper acetate;
the trivalent lanthanum salt is selected from any one or a mixture of more of lanthanum nitrate, lanthanum sulfate, lanthanum chloride or lanthanum acetate;
the complexing agent is selected from any one or more of carboxyethylenediamine, propylenediamine, butylenediamine or pentylene diamine;
the alkali is selected from any one or a mixture of a plurality of sodium hydroxide, sodium hydroxide or lithium hydroxide;
in the step 1 b), the reducing agent is selected from any one or more of water chestnut starch, lotus root starch, sweet potato starch and glutinous rice starch;
in step 2 a), the molecular formula of the silicate is Na 2 SiO 3 ·9H 2 O；
In step 3 a):
the silver complex is a mixture of silver nitrate and a ligand with the same mole as silver ions, wherein the ligand is selected from any one or more of ethylenediamine, propylenediamine, butylenediamine and pentylene diamine;
the alkali is selected from any one or a mixture of a plurality of potassium hydroxide, sodium hydroxide or lithium hydroxide.
7. A doped cuprous oxide lithium ion battery anode material prepared by the preparation method of the doped cuprous oxide lithium ion battery anode material according to any one of claims 2 to 6.
8. Use of the doped cuprous oxide lithium ion battery anode material according to claim 1 or 7, characterized in that: as a negative electrode material of a lithium ion battery.
9. A lithium ion battery comprising a battery anode, wherein the material of the battery anode comprises the doped cuprous oxide lithium ion battery anode material of claim 1 or 7.
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