CN111082039A - 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 PDF

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CN111082039A
CN111082039A CN201911202543.0A CN201911202543A CN111082039A CN 111082039 A CN111082039 A CN 111082039A CN 201911202543 A CN201911202543 A CN 201911202543A CN 111082039 A CN111082039 A CN 111082039A
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lithium ion
ion battery
solution
cuprous oxide
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CN111082039B (en
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蒋贝贝
马佳丽
聂航
赵双琪
林定文
张文博
丁先红
舒涛
聂红明
周环波
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Hubei Uee Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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 cathode material, a preparation method and application thereof, and a lithium ion battery. The preparation method comprises the following steps: 1) preparation of La3+Doping of Cu2A core of O; 2) preparing a lithium-philic layer on the surface of the core obtained in step 1); 3) 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 cathode material. The invention is doped with La3+Ion, coated with SiO2The lithium-philic layer and the metal silver conducting layer are beneficial to keeping the Cu-O bone in the process of embedding and extracting lithium ionsThe stability of the frame, the chemical stability, the conductivity and the safety of the material are kept, so that the lithium ion battery has longer service life and a cycle capacity retention rate.

Description

Cuprous oxide doped lithium ion battery cathode material, preparation method and application thereof, and lithium ion battery
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 cathode material, a preparation method and application thereof, and a lithium ion battery.
Background
Lithium ion batteries have become the most widely used secondary batteries in the 21 st century, and particularly, since the last decade, lithium ion batteries are widely used in the fields of hybrid batteries and pure electric vehicles. The negative electrode material used by the lithium ion battery manufactured by the prior art is mainly a graphite negative electrode, and the graphite negative electrode material has high capacity, stable property and low price and is one of important factors for wide application. In addition, metal oxides have been widely studied and used as negative electrode materials for lithium ion batteries, mainly due to cost and performance factors. The main metal oxides include CoO, ZnO, CuO, Cu2O、FeO、Fe2O3、TiO2、MnO2、SnO2And V2O5And so on.
The existing negative electrode material mainly has the defects of relatively low initial discharge specific capacity and short cycle life, and is particularly a 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 performance of the multi-lithium ion battery of the existing mobile electrical equipment are difficult to meet, and especially the requirements of electric automobiles on high capacity, long service life, high multiplying power and high safety of the lithium ion battery are difficult to meet.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a cuprous oxide-doped lithium ion battery cathode 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 the manufacture of various types of lithium ion batteries.
The technical scheme provided by the invention is as follows:
a cuprous oxide-doped lithium ion battery anode material comprises:
La3+doping of Cu2A core of O;
a lithium-philic layer coating the core;
and the conductive metal layer is coated outside the hydrophilic lithium layer.
In the technical scheme, the cuprous oxide-doped lithium ion battery cathode material is doped with La3+The ions are beneficial to keeping the stability of a Cu-O framework in the process of inserting and extracting the lithium ions, so that the lithium ion battery has longer service life and cycle capacity retention rate (see embodiments 2 and 4 and accompanying drawings 7 and 8-11 for details);
specifically, the La3+Doping of Cu2One possible formula for O is Cu1-xLaxO1+1.5x，0.002＜x＜0.008。
Specifically, the lithium-philic layer is SiO2Layer of, or being, SiO2A 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 SiO2Can effectively improve Li while improving the charge-discharge stability of the cathode material+The amount of insertion and release of (2) can be displayedThe specific discharge capacity of the negative active material is improved. The lithium-philic layer is SiO2Is favorable for keeping Cu2The chemical stability of O nucleus, the compatibility of negative electrode material particles with electrolyte, adhesive and the like are improved, and the improvement of Li of the negative electrode material of the cuprous oxide-doped lithium ion battery is facilitated+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 cathode material is Cu2O-coated SiO2The Ag metal coating layer with the optimal conductivity is further coated on the outer layer of the coating layer, so that the conductivity of the material can be effectively improved while the charge-discharge stability, the lithium ion insertion capacity and the discharge specific capacity of the negative electrode material are improved, and further the electrochemical performance of the negative electrode active substance and the comprehensive electrochemical performance of the manufactured lithium ion battery can be remarkably improved;
overall, the cuprous oxide-doped lithium ion battery cathode material is Cu2The density of the O metal oxide and silicon dioxide coating layer and the Ag metal layer is relatively large, the lithium ion battery cathode plate has good crystallization stability, good mechanical property and good physical and chemical stability, is easy to disperse in an aqueous solution when the cathode plate is manufactured, has better processing performance of the cathode plate, can effectively improve the compatibility of a cathode active substance and an electrolyte, is beneficial to improving the quality of the cathode plate and the performance of the lithium ion battery, and obviously improves the production efficiency of the lithium ion battery.
On the other hand, the cuprous oxide doped lithium ion battery cathode material is Cu2O-coated SiO2The outer layer of the coating layer is also coated with an Ag metal coating layer, and simultaneously, the SiO layer2Has extremely high chemical stability, is difficult to decompose and release oxygen, Ag has good conductivity and electrochemical stability in the electrochemical environment of the lithium ion battery, the Ag and the Ag are respectively positioned on the outer layer and the secondary outer layer of the cathode material, and SiO can increase the lithium ion insertion amount, namely the cathode capacity of the battery while the silica can increase the lithium ion insertion amount2And the metallic silver coating layer effectively strengthens Cu2Safety performance of O cathode material or greatly eliminating lithium ion battery possibly caused by cathode active materialPotential safety hazard.
On the other hand, compared with the graphite negative electrode material, the cuprous oxide-doped lithium ion battery negative electrode material has obviously higher tap density and higher adhesion or bonding performance with a copper foil current collector, so that the phenomena of powder falling and powder falling of a pole piece can be greatly reduced under the condition of properly reducing the using amount of the adhesive, the dust pollution to the production environment can be effectively reduced in the manufacturing process of the lithium ion battery negative electrode, the production efficiency of the lithium ion battery and the product quality of the negative pole piece are obviously improved, and the environmental efficiency of battery production is also improved.
The invention also provides a preparation method of the cuprous oxide-doped lithium ion battery cathode material, which comprises the following steps:
1) preparation of La3+Doping of Cu2A core of O;
2) preparing a lithium-philic layer on the surface of the core obtained in step 1);
3) 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 cathode material.
Based on the technical scheme, the cuprous oxide doped lithium ion battery cathode material can be prepared, and has the beneficial effects.
Specifically, 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 in the complex mixture, Cu2+Is 0.1 to 1.0M (mol/L) of Cu2+And La3+In a molar ratio of 100:0.2 to 100:0.8, Cu2+The molar ratio of the water-soluble organic acid to the compounding agent is 1: 0.99-1: 1.01, an alkali solution with the concentration of 0.1-0.5M is added, and the mixture is 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 1a), and stirring at 45-75 ℃ for reaction to obtain the La-containing solution3+Doping of Cu2A 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) comprises the following steps:
2a) adding silicate powder into the mixture solution obtained in the step 1b), and stirring for dispersing;
2b) after the silicate is uniformly dispersed, adding hydrochloric acid with the concentration of 0.2-1.0M, and continuously stirring for reaction;
2c) standing for aging after the reaction is finished, centrifuging the mixture to remove the solution after the aging is finished, leaching the obtained precipitate with 0.01M aqueous alkali for 3 to 5 times to obtain La coated with silicic acid3+Doping of Cu2Precipitating O;
wherein, based on the amount of the complex mixture in the step 1a), 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.
Specifically, the step 3) includes the following steps:
3a) la of the coated silicic acid obtained in step 2c)3+Doping of Cu2Adding the O precipitate into a silver complex solution with the concentration of 0.1-0.25M, sequentially adding a reducing agent solution with the concentration of 3-10 wt% and an alkali solution with the concentration of 0.1-0.5M, stirring at 45-75 ℃ for reaction, performing centrifugal separation after the reaction to obtain a precipitate, washing the precipitate with water until the pH value of an eluate is neutral (pH is 6.8-7.2), and obtaining the Ag-coated SiO2Coated La3+Doping of Cu2O；
3b) Coating the Ag obtained in step 3a) with SiO2Coated La3+Doping of Cu2Roasting the O for 4-12 hours at the temperature of 180-300 ℃ to obtain a cuprous oxide-doped lithium ion battery cathode material;
wherein the volume ratio of the complex mixture, the silver complex solution, the raw agent solution and the alkali solution is 50-500: 10-100: 5-30: 2-10 based on the amount of the complex mixture in the step 1 a).
Specifically, in step 1 a): the cupric salt is selected from any one or more of cupric nitrate, cupric sulfate, cupric chloride or cupric acetate.
Specifically, in step 1 a): the trivalent lanthanum salt is selected from one or more of lanthanum nitrate, lanthanum sulfate, lanthanum chloride or lanthanum acetate;
specifically, in step 1 a): the compounding ingredient is selected from one or more of carboxyethylenediamine, propylenediamine, butylenediamine or pentylenediamine;
specifically, in step 1 a): the alkali is selected from any one or more of potassium hydroxide, sodium hydroxide or lithium hydroxide;
specifically, in the step 1b), 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 the reduction of Ag+Forming an Ag coating layer efficiently;
specifically, in the step 2a), the molecular formula of the silicate is Na2SiO3·9H2O；
Specifically, in step 3 a): the silver complex is a mixture of silver nitrate and a ligand which is equimolar with silver ions, and the ligand is selected from any one or more of ethylenediamine, propylenediamine, butylenediamine or pentylenediamine;
specifically, in step 3 a): the alkali is selected from any one or more of sodium hydroxide, sodium hydroxide or lithium hydroxide.
Based on the technical scheme, the preparation method of the cuprous oxide doped lithium ion battery cathode material has the advantages of relatively simple process technology, simple equipment, high production efficiency, abundant and easily-obtained main raw materials, easy recycling of byproducts, no pollution or low pollution of wastes, 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:
the first step is to 50 to 500mLCu2+Cu at a concentration of 0.1 to 1.0M (mol/L, the same applies hereinafter)2+:La3+Copper salt and lanthanum salt in a molar ratio of 100: 0.2-100: 0.8 to Cu2+Adding 5-30 mL of 0.1-0.5M alkali solution into a mixture (hereinafter referred to as a compound) solution of a complex of an equimolar compounding agent, and stirring and mixing uniformly to obtain a mixed solution;
secondly, adding 10-60 mL of reducing agent solution with the concentration of 5-15 wt% and 5-30 mL of organic acid solution with the concentration of 0.1-0.5M into the mixed solution in the first step, and stirring for 10-45 minutes at 45-75 ℃;
thirdly, adding 0.5-7.5 g of silicate powder into the mixture solution obtained in the second step, stirring for 3-15 minutes, adding 10-50 mL of hydrochloric acid with the concentration of 0.2-1.0M, and continuously stirring for 25-55 minutes; standing for 5-25 minutes, centrifuging the mixture to separate out the solution, leaching the precipitate for 3-5 times by using 0.01M aqueous alkali to obtain the doped La coated with silicic acid3+Ionic Cu2Depositing cuprous oxide;
fourthly, 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 ℃, performing centrifugal separation, washing the precipitate with water until the pH value of an eluate is neutral (about pH 7.0, or 6.8, 7.0 or 7.2), washing the silver-coated simple substance and silica-coated La-coated simple substance3+Doping of Cu2O negative electrode material, namely a modified cuprous oxide lithium ion battery negative electrode material. And roasting the precipitate for 4-12 hours at the temperature of 180-300 ℃ to obtain the cuprous oxide-doped lithium ion battery cathode material.
The invention also provides the cuprous oxide-doped lithium ion battery cathode material prepared by the preparation method.
The cuprous oxide doped lithium ion battery cathode material provided by the technical scheme has wider particle size distribution, the particle size range is 100 nm-2.5 mu m, and the particle size mainly depends on the content of doped ions,The coating amount of silicon dioxide and metal Ag and the preparation specific process parameters of the material are controlled, the doping ion amount, the coating amount of silicon dioxide and metal silver and the coating thickness are all easy to control, and the prepared doped Cu is easy to control2The particle size of the O negative electrode material (see the embodiment 1-embodiment 4 and the attached figures 1-4 in the specification for details);
the cuprous oxide-doped lithium ion battery cathode material provided by the technical scheme is polyhedral particles with large specific surface area, is favorable for contact compatibility of active substances and electrolyte, improves the wetting efficiency of the electrolyte, improves the electrochemical properties of an electrode and a lithium ion battery, is favorable for full contact of the cathode material and a conductive agent, an adhesive, a solvent and the like due to the polyhedral shape, is favorable for improving the production efficiency of cathode slurry, and further improves the Cu content2The electrochemical performance of the O active material is integrated with the electrochemical performance of the battery (see the embodiment 3-embodiment 4 and the attached figures 3-4 in the specification for details).
La of cuprous oxide doped lithium ion battery cathode material provided by the technical scheme3+The doping amount, the particle size of the silicon dioxide, the thickness and the content of the silicon dioxide and the metal Ag coating layer and the like are easy to control, and the La can be prepared according to the requirements of different types of lithium ion batteries (rate type lithium ion batteries, capacity type lithium ion batteries and the like)3+Cu with certain differences in doping amount, silicon dioxide and metal Ag coating amount, particle size and comprehensive electrochemical performance2And O, a 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 the cuprous oxide doped lithium ion battery cathode material has higher charge-discharge specific capacity and high-rate discharge effect, and the Cu has high specific capacity and high-rate discharge effect2The highest first discharge specific capacity of the O negative electrode material reaches 668mAh/g (see embodiment 2 in detail), and the highest first discharge specific capacity of the commercial graphite is 348mAh/g (the theoretical capacity of the graphite is 370mAh/g, see figure 8 in detail); capacity retention rate of 1000 charge-discharge cycles at 1C rate of not less than 90% (see examples 2 and 4, and figure 7AB for details), of comparative sampleThe capacity retention rate of 665-time charge-discharge cycles is 69.5% (see figure 7C for details); 1180 discharge efficiencies reached 93.77% and 90.8% over the charge-discharge cycle (see examples 2, 4, fig. 8AB for details), while 786 cycles of the comparative sample only reached 73.54% (see fig. 8C 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 (ternary) lithium nickel cobalt manganese oxide, the capacity of the battery formed by the positive electrode material can reach 99% of the designed capacity, the nominal voltage can reach more than 3.7V, and the requirement of single battery voltage is met.
Drawings
FIG. 1 shows a Cu-doped alloy prepared in example 12SEM photo of cathode material of O lithium ion battery;
FIG. 2 shows a Cu-doped alloy prepared in example 22SEM photo of cathode material of O lithium ion battery;
FIG. 3 shows a Cu-doped alloy prepared in example 22An XRD curve of the cathode material of the O lithium ion battery;
FIG. 4 shows a Cu-doped alloy prepared in example 32SEM photo of cathode material of O lithium ion battery;
FIG. 5 shows a Cu-doped alloy prepared in example 42SEM photo of cathode material of O lithium ion battery;
FIG. 6 shows a Cu-doped alloy prepared in example 42An XRD curve of the cathode material of the O lithium ion battery;
FIG. 7 shows a Cu-doped alloy prepared in example 22The charge-discharge capacity rate of the O negative electrode material;
FIG. 8 shows a Cu-doped alloy prepared in example 42Charge-discharge cycle discharge efficiency of the O negative electrode material.
Wherein: in fig. 7 and 8, A, B represents the samples prepared in examples 2 and 4, respectively, and C represents a comparative graphite sample.
FIG. 9 shows a Cu-doped layer prepared in example 12The 1C rate of the O negative electrode material is used for measuring the initial charge-discharge performance of the battery.
FIG. 10 shows a Cu-doped layer prepared in example 12And 2C multiplying power of the O negative electrode material is used for measuring the cycle performance of the battery.
FIG. 11 shows a Cu dopant prepared in example 12And (3) measuring the high-rate cycle performance diagram of the battery at the 5C rate of the O negative electrode material.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
Doped cladding doped Cu2The preparation method of the O negative electrode material comprises the following steps:
first, 50mLCu2+The concentration is 0.1M, Cu2+:La3+Adding 5mL of 0.1M potassium hydroxide solution into a compound solution of copper nitric acid, lanthanum nitrate and ethylenediamine with the molar ratio of 100:0.2 and the molar ratio of 5 millimoles (about 0.34g), and uniformly stirring and mixing;
secondly, adding 10mL of water chestnut starch reducing agent solution with the concentration of 5 wt% and 5mL of acetic acid solution with the concentration of 0.1M into the mixed solution, and stirring and reacting for 45 minutes at 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 to stir for 25 minutes; standing for 5 minutes, centrifuging the mixture to separate out the solution, leaching the precipitate for 3-5 times by using 0.01M potassium hydroxide solution to obtain the doped La coated with silicic acid3+Cu of (2)2Precipitating O;
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 3 wt%, adding 2mL of potassium hydroxide solution with the concentration of 0.1M, 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 silica-coated La with the surface coated with the silver simple substance3+Doping of Cu2O negative electrode material, i.e. oneSeed doped Cu2And O, a 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 the techniques of SEM, EDS, XRD and the like, and the obtained doped Cu2The O negative electrode material is mainly polyhedral particles, the particle size range of the O negative electrode material is about 0.1-1.5 mu m, the average particle size is about 0.65 mu m (detailed in figure 1), and La3+The doping amount (Cu: La atomic ratio) is about 1000:1.81, and the silicon dioxide coating amount (Cu: Si atomic ratio) is about 100: 23.7; the Ag coating amount (Cu: Ag atomic ratio) is about 100:12.9, and the synthesized doped Cu2O is a cubic face-centered crystal; under the condition of 1C multiplying power, the initial discharge specific capacity of the cuprous oxide negative electrode active substance is 651mAh/g, and specific electrical property tests are shown in example 5 and attached figures 9-11).
Example 2
Doped cladding doped Cu2The preparation method of the O negative electrode material comprises the following steps:
first, 100mLCu is added2+The concentration is 0.3M, Cu2+:La3+Adding 10mL of 0.2M sodium hydroxide solution into a compound solution of copper sulfate, lanthanum sulfate and 30 millimoles of propylene diamine in a molar ratio of 100:0.4, and uniformly stirring and mixing;
secondly, adding 10mL of lotus root starch reducing agent solution with the concentration of 8 wt% into the mixed solution, adding 10mL of 1.0M propionic acid solution, and stirring for 35 minutes at 55 ℃;
step three, adding 1.5g of sodium silicate powder into the mixture solution obtained in the step two, stirring for 6 minutes, adding 15mL of 0.4M hydrochloric acid, and continuing to stir for 35 minutes; standing for 10 minutes, centrifuging the mixture to separate out the solution, leaching the precipitate for 3-5 times by using 0.01M sodium hydroxide solution to obtain the doped La coated with silicic acid3+Ionic Cu2Precipitating O;
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 5 wt%, stirring for 15 minutes at 65 ℃, performing centrifugal separation, washing the precipitate with water until the pH value of an eluate is neutral, and roasting the washed precipitate for 8 hours at 220 ℃ to obtain a simple substance with silver coated on the surfaceOf La coated with silicon dioxide3+Doping of Cu2O negative electrode material, i.e. Cu doped2And O, a negative electrode material.
The shape, the grain diameter, the atomic ratio and the crystal structure of the synthesized modified cuprous oxide cathode material are respectively measured by SEM, EDS, XRD and the like, and the obtained doped Cu2The O negative electrode material is mainly polyhedral particles, the particle size range of the O negative electrode material is about 0.2-2.0 mu m, the average particle size is about 1.0 mu m (see the attached figure 2 for details), and La3+The doping amount (Cu: La atomic ratio) is about 1000:3.53, and the silicon dioxide coating amount (Cu: Si atomic ratio) is about 100: 13.3; the Ag coating amount (Cu: Ag atomic ratio) is about 100:10.4, and the synthesized doped Cu2O is a cubic face-centered crystal (shown in figure 3); under the condition of 1C multiplying power, the initial discharge specific capacity of the cuprous oxide negative electrode active substance is 668mAh/g, the capacity retention rate of 1000 charge-discharge cycles is 91.8% (detailed in figure 7A), and the capacity retention rate of a comparative sample of 665 charge-discharge cycles is 69.5% (detailed in figure 7C); 1180 discharge cycles of 93.77% (see fig. 8A for details) and 786 cycles of the comparative sample had an efficiency of 73.54% (see fig. 8C for details).
Example 3
Doped cladding doped Cu2The preparation method of the O negative electrode material comprises the following steps:
first, to 200mLCu2+The concentration is 0.75M, Cu2+:La3+Adding 20mL of 0.3M lithium hydroxide solution into a compound solution of copper chloride, lanthanum chloride and ammonium butanediamine with the molar ratio of 100:0.6, and stirring and mixing uniformly;
secondly, adding 40mL of sweet potato starch solution with the concentration of 12 wt% into the mixed solution, adding 20mL of butyric acid solution with the concentration of 0.3M, and stirring for 25 minutes at 65 ℃;
step three, adding 4.0g of sodium silicate powder into the mixture solution obtained in the step two, stirring for 12 minutes, adding 30mL of hydrochloric acid with the concentration of 0.8M, and continuing to stir for 45 minutes; standing for 20 minutes, centrifuging the mixture to separate out the solution, leaching the precipitate for 3-5 times by using 0.01M lithium hydroxide solution to obtain the doped La coated with silicic acid3+Ionic Cu2Precipitating O;
fourthly, 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 8 wt%, stirring for 20 minutes at 55 ℃, performing centrifugal separation, washing the precipitate with water until the pH value of an eluate is neutral, and roasting the washed precipitate for 6 hours at 260 ℃ to obtain the silica-coated La with the surface coated with the silver simple substance3+Doping of Cu2O negative electrode material, i.e. Cu doped2And O, a negative electrode material.
The shape, the grain diameter, the atomic ratio and the crystal structure of the synthesized modified cuprous oxide cathode material are respectively measured by SEM, EDS, XRD and the like, and the obtained doped Cu2The O negative electrode material is mainly polyhedral particles, the particle size range of the O negative electrode material is about 0.25-2.0 mu m, the average particle size is about 1.25 mu m (see the attached figure 4 for details), and La3+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 Ag coating amount (Cu: Ag atomic ratio) is about 100:6.8, and the synthesized doped Cu2And O is a cubic face-centered crystal. Under the condition of 1C multiplying power, the initial discharge specific capacity of the cuprous oxide negative electrode active substance is 625 mAh/g.
Example 4
Doped cladding doped Cu2The preparation method of the O negative electrode material comprises the following steps:
first, the process is carried out in the direction of 500mLCu2+The concentration is 1.0M, Cu2+:La3+Adding 30mL of 0.5M sodium hydroxide solution into a compound solution of copper acetate, lanthanum acetate and 0.5 mol of pentamethylene diamine in a molar ratio of 100:0.8, and stirring and mixing uniformly;
secondly, adding 60mL of 15 wt% glutinous rice starch solution and 30mL of 0.5M succinic acid solution into the mixed solution, and stirring for 10 minutes at 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 to stir for 55 minutes; standing for 25 minutes, centrifuging the mixture to separate out the solution, leaching the precipitate for 3-5 times by using 0.01M sodium hydroxide solution to obtain the doped La coated with the silicic acid3+Ionic Cu2Precipitating O;
fourthly, adding the precipitate obtained in the third step into 250mL of silver complex solution with the concentration of 0.05M, adding 300mL of reducing agent solution with the concentration of 10 wt%, stirring for 5 minutes at 50 ℃, performing centrifugal separation, washing the precipitate with water until the pH value of an eluate is neutral, and roasting the washed precipitate for 4 hours at 300 ℃ to obtain the silica-coated La with the surface coated with the silver simple substance3+Doping of Cu2O negative electrode material, i.e. Cu doped2And O, a negative electrode material.
The shape, the grain diameter, the atomic ratio and the crystal structure of the synthesized modified cuprous oxide cathode material are respectively measured by SEM, EDS, XRD and the like, and the obtained doped Cu2The O negative electrode material is mainly polyhedral particles, the particle size range of the O negative electrode material is about 0.5-2.5 mu m, the average particle size is about 1.5 mu m (see the attached figure 5 for details), and La is3+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 Ag coating amount (Cu: Ag atomic ratio) is about 100:3.6, and the synthesized doped Cu2O is a 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 negative active material is 649mAh/g, the capacity retention rate of 1000 charge-discharge cycles is 90.8% (see the detailed drawing in figure 7B), the capacity retention rate of 665 charge-discharge cycles of the comparative sample is 69.5% (see the detailed drawing in figure 7C), the capacity retention rate of 1180 cycles of charge-discharge cycles is 90.8% (see the detailed drawing in figure 8B), and the 786 cycles of the comparative sample is 73.54% (see the detailed drawing in figure 8C).
Example 5
With the cuprous oxide negative electrode active material synthesized in example 1 of the present invention, the ratio of the cuprous oxide negative electrode active material: conductive agent (acetylene black): the mass ratio of a binding agent (SBR) is 93-96: 2.5-4.5: 1.5-2.5, a negative electrode is manufactured, a positive active substance is a nickel lithium manganate ternary material (the positive electrode capacity surplus coefficient is designed to be 1.15, namely the positive electrode design formula capacity is larger than the negative electrode formula capacity by 15%), the manufactured 112535 type soft package lithium ion test battery with the capacity of 1000mAh is used for measuring the initial charge-discharge performance of the battery at a 1C multiplying power, the cycle performance of the battery at a 2C multiplying power and the high-multiplying-power cycle performance of the battery at a 5C multiplying power under the conditions that the charge limiting voltage is 4.2V and the discharge cut-off voltage is 3.0V. The test open circuit voltage and the internal resistance are respectively in the ranges of 3.82-3.915V and 11.34-26.45 m omega. The first charge-discharge specific capacity of the test battery 1C is 651mAh/g, the 891 th cyclic discharge efficiency is more than 99%, the 2557 th cyclic discharge efficiency is more than 90% (the 2558 th cyclic discharge efficiency is 89.88%), and the 1C multiplying power cycle life (the discharge efficiency is calculated to be less than 75%) exceeds the 2558 th cycle (detailed in figure 9); test battery 2C rate charge-discharge cycle efficiency: the discharge efficiency of the 570 th cycle is more than 99%, the discharge efficiency of the 1280 th cycle is more than 95%, the discharge efficiency of the 2011 th cycle is more than 90% (the discharge efficiency of the 2012 cycles is 89.92%), and the 2C multiplying power cycle life (calculated by the discharge efficiency of less than 75%) exceeds the 2012 cycles (see the detailed figure 10); test battery 5C rate charge-discharge cycle efficiency: the 330 th cycle discharge efficiency is greater than 95%, the 1050 th cycle discharge efficiency is greater than 90%, the 1652 th cycle discharge efficiency is greater than 80% (the 1653 th cycle discharge efficiency is 79.96%), and the 5C-rate cycle life (calculated with the discharge efficiency less than 75%) exceeds 1653 cycles (see figure 11 in detail).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The cuprous oxide-doped lithium ion battery cathode material is characterized by comprising the following components in parts by weight:
La3+doping of Cu2A core of O;
a lithium-philic layer coating the core;
and the conductive metal layer is coated outside the hydrophilic lithium layer.
2. The cuprous oxide-doped lithium ion battery negative electrode material of claim 1, wherein:
the lithium-philic layer is SiO2Layer of, or being, SiO2A mixed layer with silicic acid;
the conductive metal layer is an Ag layer.
3. The preparation method of the cuprous oxide-doped lithium ion battery cathode material is characterized by comprising the following steps of:
1) preparation of La3+Doping of Cu2A core of O;
2) preparing a lithium-philic layer on the surface of the core obtained in step 1);
3) 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 cathode material.
4. The preparation method of the cuprous oxide-doped lithium ion battery anode material according to claim 3, 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 in the complex mixture, Cu2+Is 0.1 to 1.0M, Cu2+And La3+In a molar ratio of 100:0.2 to 100:0.8, Cu2+The molar ratio of the water-soluble organic acid to the compounding agent is 1: 0.99-1: 1.01, an alkali solution with the concentration of 0.1-0.5M is added, and the mixture is 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 1a), and stirring at 45-75 ℃ for reaction to obtain the La-containing solution3+Doping of Cu2A 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.
5. The preparation method of the cuprous oxide-doped lithium ion battery anode material according to claim 4, wherein the step 2) comprises the following steps:
2a) adding silicate powder into the mixture solution obtained in the step 1b), and stirring for dispersing;
2b) after the silicate is uniformly dispersed, adding hydrochloric acid with the concentration of 0.2-1.0M, and continuously stirring for reaction;
2c) standing for aging after the reaction is finished, centrifuging the mixture after the aging is finished to remove the solution, leaching the obtained precipitate with 0.01M aqueous alkali for a plurality of times to obtain La coated with silicic acid3+Doping of Cu2Precipitating O;
wherein, based on the amount of the complex mixture in the step 1a), 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.
6. The preparation method of the cuprous oxide-doped lithium ion battery anode material according to claim 5, wherein the step 3) comprises the following steps:
3a) la of the coated silicic acid obtained in step 2c)3+Doping of Cu2Adding the O precipitate into a silver complex solution with the concentration of 0.1-0.25M, sequentially adding a reducing agent solution with the concentration of 3-10 wt% and an alkali solution with the concentration of 0.1-0.5M, stirring at 45-75 ℃ for reaction, performing centrifugal separation after the reaction to obtain a precipitate, washing the precipitate with water until the pH value of an eluate is neutral, and obtaining the La coated with Ag-coated silicic acid3+Doping of Cu2O；
3b) Coating the Ag obtained in step 3a) with SiO2Coated La3+Doping of Cu2Roasting the O for 4-12 hours at the temperature of 180-300 ℃ to obtain a cuprous oxide-doped lithium ion battery cathode material;
wherein the volume ratio of the complex mixture, the silver complex solution, the raw agent solution and the alkali solution is 50-500: 10-100: 5-30: 2-10 based on the amount of the complex mixture in the step 1 a).
7. The preparation method of the cuprous oxide-doped lithium ion battery negative electrode material according to claim 6, wherein the method comprises the following steps:
in step 1 a):
the cupric salt is selected from one or more of cupric nitrate, cupric sulfate, cupric chloride or cupric acetate;
the trivalent lanthanum salt is selected from one or more of lanthanum nitrate, lanthanum sulfate, lanthanum chloride or lanthanum acetate;
the compounding ingredient is selected from one or more of carboxyethylenediamine, propylenediamine, butylenediamine or pentylenediamine;
the alkali is selected from any one or more of sodium hydroxide, sodium hydroxide or lithium hydroxide;
in the step 1b), the reducing agent is selected from one or more of water chestnut starch, lotus root starch, sweet potato starch or glutinous rice starch;
in step 2a), the molecular formula of the silicate is Na2SiO3·9H2O；
In step 3 a):
the silver complex is a mixture of silver nitrate and a ligand which is equimolar with silver ions, and the ligand is selected from any one or more of ethylenediamine, propylenediamine, butylenediamine or pentylenediamine;
the alkali is selected from any one or more of potassium hydroxide, sodium hydroxide or lithium hydroxide.
8. The doped cuprous oxide lithium ion battery negative electrode material prepared by the preparation method of the doped cuprous oxide lithium ion battery negative electrode material according to any one of claims 3 to 7.
9. Use of a doped cuprous oxide lithium ion battery anode material according to claim 1 or 2 or 8, wherein: as the cathode material of the lithium ion battery.
10. A lithium ion battery comprising a battery negative electrode, wherein the material of the battery negative electrode comprises the lithium ion battery negative electrode material of claim 9.
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