CN108172814A - A kind of silver simple substance coating spinelle type LiMn2O4Composite material and preparation method thereof - Google Patents

A kind of silver simple substance coating spinelle type LiMn2O4Composite material and preparation method thereof Download PDF

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CN108172814A
CN108172814A CN201810104244.2A CN201810104244A CN108172814A CN 108172814 A CN108172814 A CN 108172814A CN 201810104244 A CN201810104244 A CN 201810104244A CN 108172814 A CN108172814 A CN 108172814A
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silver
limn
simple substance
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composite material
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CN108172814B (en
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郭俊明
黄技军
郭昱娇
苏长伟
刘晓芳
白玮
向明武
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Yunnan Minzu University
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of silver-colored simple substance coating spinelle type LiMn2O4Composite material preparation method, the preparation method include prepare silver nitrate solution, prepare presoma with heating burning and etc..Compared with prior art, the present invention has quickly prepares target product, and simple process and low cost is honest and clean at low temperature, easily realizes the advantageous effects such as industrialized production.

Description

A kind of silver simple substance coating spinelle type LiMn2O4Composite material and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion.More particularly it relates to a kind of silver simple substance coating spinelle Type LiMn2O4Composite material, further relate to the silver-colored simple substance coating spinelle type LiMn2O4Composite material preparation method.
Background technology
Lithium ion battery is a kind of environmentally protective battery, positive electrode be manufacture lithium ion battery critical material it One.The positive electrode for using and studying at present is mainly cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), LiFePO 4 (LiFePO4) and lithium manganate having spinel structure (LiMn2O4) etc. materials.Wherein LiMn 2O4It is a kind of lithium ion battery in the ascendant Positive electrode has many advantages, such as that nontoxic, safety is good, non-environmental-pollution, operating voltage is high, of low cost, thermal stability is high, because This most possibly substitutes the LiCoO having been commercialized2Positive electrode.However, LiMn2O4 capacity attenuation is a fatal obstacle, limit Its large-scale use has been made, it is especially true at high temperature.It is widely investigated LiMn2O4 capacity rapid decay reason, one It is in manganese ion dissolution to electrolyte, the second is can be decomposed in high potential region electrolyte, the third is Jahn-Teller distorts. Recently, in order to eliminate this capacity rapid decay, people employ ion doping（Such as aluminium, cobalt, chromium, nickel, iron）Spinelle Type LiMn2O4 (LiMn2O4) or use different materials（Such as titanium dioxide, magnesia, lithium aluminate, aluminium oxide）Surface coats mangaic acid Lithium.For example, CN106784682 A disclose titanium oxide, silica, aluminum oxide metal oxide coating spinelle type LiMn2O4 Preparation method.This method includes adding in LiMn2O4 in absolute ethyl alcohol, and add in concentrated ammonia liquor, and ultrasonic disperse is uniform；By metal oxygen Compound presoma is added in absolute ethyl alcohol, and ultrasonic disperse is uniform；Precursor solution is taken to be added dropwise in LiMn2O4 solution, and is heated Stirring；Above-mentioned mixed solution centrifuge washing is dried again, and the LiMn2O4 of metal oxide cladding is obtained after calcining.CN 104900855 A disclose a kind of preparation method of manganate cathode material for lithium, which coats one layer by LiMn2O4 surface Nickel coating is formed；Preparation method be by LiMn2O4 under the action of the dispersant successively after sensitization plays, activation, reduction treatment, Plate nickel coating；The LiMn2O4 for having plated nickel coating is heat-treated again, obtains nickel coated manganate cathode material for lithium.CN 103996840 A provide a kind of preparation method for coating LiMn2O4, and this method includes preparing metal oxide；By LiMn2O4 plus Enter in water, be dispersed with stirring to form suspension, and it is 6~8 to adjust suspension pH value；The metal oxide of preparation is added in described outstanding In turbid；Product centrifuge washing is dried, and titanium dioxide, silica, aluminium oxide, lanthanum sesquioxide or three are obtained through calcining Aoxidize two ferroelectric metal oxides cladding LiMn2O4.But there are preparation process is complicated, step is more, some is gone back for these prior arts Use the technological deficiencies such as organic solvent.In the several years in past, some researchers use deposition of silver method jacketed electrode material（Such as phosphorus Sour iron lithium, cobalt acid lithium and lithium titanate）, certain progress is achieved, improves chemical property.
For this purpose, for technological deficiency of the existing technology, the present inventor passes through on the basis for summarizing the prior art Lot of experiments and analysis, complete the present invention finally.
Invention content
Technical problems to be solved]
The object of the present invention is to provide a kind of silver-colored simple substance coating spinelle type LiMn2O4Composite material.
It is a further object to provide the silver-colored simple substance coating spinelle type LiMn2O4Composite material preparation Method.
Technical solution]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of silver-colored simple substance coating spinelle type LiMn2O4Composite material preparation method.
The step of preparation method, is as follows：
A, silver nitrate solution is prepared
Silver nitrate is dissolved in distilled water, be prepared it is a concentration of by weight 0.5~2.0% silver nitrate solution；
B, presoma is prepared
Spinel-type LiMn2O4With glucose according to weight ratio 10：0.5~1.0 is uniformly mixed, and is then added to the mixture In the silver nitrate solution that step A is obtained, wherein LiMn2O4It is 1 with weight ratio silver-colored in silver nitrate：0.02~0.10, it is stirred Make spinel-type LiMn2O4It is uniformly dispersed, obtains a kind of slurry mix, then heating evaporation removes moisture, obtains a kind of forerunner Body；
C, heating burning
The presoma obtained in step B is allowed to carry out heating combustion reaction under conditions of 500~600 DEG C of air and temperature, is obtained The silver-colored simple substance coating spinelle type LiMn2O4Composite material.
According to another preferred method of implementation of the present invention, in stepb, it is stirred using blender with 30~60rpm of rotating speed Mix 1.8~2.2h of mixing.
According to another preferred method of implementation of the present invention, in stepb, the slurry mix in drying box 1.0~2.0h of heat drying under conditions of 100~105 DEG C of temperature.
According to another preferred method of implementation of the present invention, in stepb, the water content of the presoma is by weight 0.5~2.0%.
According to another preferred method of implementation of the present invention, in step C, the heating burning that step B obtains presoma is anti- It is 1.0~1.5h between seasonable.
The invention further relates to the silver-colored simple substance coating spinelle type LiMn that the preparation method is prepared2O4Composite material.
A preferred embodiment of the invention, the silver simple substance coating spinelle type LiMn2O4Composite material Particle size is 0.2~2.0 μm.
According to another preferred method of implementation of the present invention, silver-colored simple substance is only coated on LiMn2O4On particle surface, silver Content is by weight 2~10%.
The present invention is described in more detail below.
The present invention relates to a kind of silver-colored simple substance coating spinelle type LiMn2O4Composite material preparation method.
The step of preparation method, is as follows：
A, silver nitrate solution is prepared
Silver nitrate is dissolved in distilled water, be prepared it is a concentration of by weight 0.5~2.0% silver nitrate solution；
In the present invention, if the concentration of silver nitrate solution is less than 0.5%, silver nitrate solution adds in excessively, causes step C's Slurry mix is excessively dilute；If the concentration of silver nitrate solution is higher than 2.0%, it is unfavorable for accurately controlling the amount for adding in silver nitrate；Cause This, a concentration of the 0.5~2.0% of silver nitrate solution be it is appropriate, preferably 0.8~1.6%, more preferably 1.0~1.4%.
B, presoma is prepared
Spinel-type LiMn2O4With glucose according to weight ratio 10：0.5~1.0 is uniformly mixed, and is then added to the mixture In the silver nitrate solution that step A is obtained, wherein LiMn2O4It is 1 with weight ratio silver-colored in silver nitrate：0.02~0.10, it is stirred Make spinel-type LiMn2O4It is uniformly dispersed, obtains a kind of slurry mix, then heating evaporation removes moisture, obtains a kind of forerunner Body；
The spinel-type LiMn that the present invention uses2O4It is current market sales of product, such as limited by great gram of Beijing science and technology Company is with trade name LiMn2O4 LiMn2O4The product of sale or according to document Xianyan Zhou et al. Solid- state combustion synthesis of spinel LiMn2O4 using glucose as a fuel[J]. Ceramics International, 2013, 39:4783-4789 or Yan Xia et al. Modification of the Solution Flameless Combustion Synthesis of Spinel LiMn2O4 by Nitric Acid [J]. Asian Journal of Chemistry, 2013, 25(4):1917-1920 or Jintao Liu et al. Enhanced cycle and rate performances of Li(Li0.05Al0.05Mn1.90)O4 cathode material prepared via a solution combustion method for lithium-ion batteries [J]. Solid State Ionics, 2017, 307:79-89 or Wangqiong Xu et al. Preparation and Electrochemical Performance of NanoLiNi0.05Mn1.95O4 Cathode Materials by a Low-Temperature Molten-Salt Combustion Method[J]. International Journal of Electrochemical Science,2017, 12:Prepared by the method for 9758-9773 descriptions, and using X-ray diffraction Analysis method is determined as the substance of spinel structure.
Glucose is aldohexose, and white crystal is soluble easily in water, and 146 DEG C of fusing point, glucose molecule contains aldehyde radical, is had also Originality, silver ion reduction can be in the solution elemental silver, while system temperature is made to increase in combustion by it, accelerate nitric acid Silver is decomposed into elemental silver, and glucose burning generates carbon dioxide and water.In the present invention, the basic role of glucose is to occur Burning, quickly improves temperature, and silver nitrate is made quickly to occur to generate the decomposition reaction of elemental silver.LiMn2O4With the weight ratio of glucose It is 10：0.5~1.0, if LiMn2O4It is more than 10 with the weight ratio of glucose：0.5, then fuel is few, it is impossible to make reaction system fast Speed heating；If LiMn2O4It is less than 10 with the weight ratio of glucose：1.0, then excessive fuel, causes waste of fuel；Preferably, it is sharp Spar type LiMn2O4Weight ratio with glucose is 10：0.6~0.8.
LiMn2O4With weight ratio 1 silver-colored in silver nitrate：0.02~0.10.If LiMn2O4With weight silver-colored in silver nitrate Than being more than 10：0.02, then coating spinelle type LiMn2O4Silver content it is inadequate, it is impossible to complete cladding；If LiMn2O4With silver nitrate The weight ratio of middle silver is less than 10：0.10, then coating spinelle type LiMn2O4Silver content it is too many, part cladding silver it is thicker, can drop Low LiMn2O4The chemical property of positive electrode；Preferably, spinel-type LiMn2O4It is 10 with weight ratio silver-colored in silver nitrate： 0.04~0.08.
In this step, 1.8~2.2h is stirred with 30~60 rpm of rotating speed using blender.If mixing speed With mixing time be more than the range be all worthless because the mixing of each substance cannot be made to reach optimum state.
In this step, which heats 1.0~2.0h in drying box at 105 DEG C of temperature, before obtaining The water content for driving body is by weight 0.5~2.0%.If heating time is more than this range, i.e. heating time is too short or long All cannot by presoma water content control in the range of 0.5~2.0%, forerunner's body water content be more than this range be it is unfavorable, this It is because the temperature when water content of presoma can partly prevent the mixture from burning is excessively high.
Blender that the present invention uses, drying box are all current market sales of products, such as (domestic by German IKA It is joint) company sold with 104 electronic stirrers of trade name RW blender, by Shanghai Yiheng Scientific Instruments Co., Ltd with quotient The drying box of name of an article electric drying oven with forced convection sale.
C, heating burning
The presoma obtained in step B is allowed to carry out heating combustion reaction under conditions of 500~600 DEG C of air and temperature, is obtained The silver-colored simple substance coating spinelle type LiMn2O4Composite material.
In this step, step B obtains presoma heating burning 1.0 under conditions of 500~600 DEG C of air and temperature ~1.5h.
When heating burning time as 1.0~1.5h, if ignition temperature is less than 500 DEG C, silver nitrate decomposes incomplete；Such as Fruit ignition temperature is higher than 600 DEG C, then causes energy waste, cost raising；Therefore, ignition temperature is reasonable for 500~600 DEG C 's；Preferably 520~580 DEG C, more preferably 540~560 DEG C.The presoma is in 500 DEG C and 550 DEG C of air and temperature Under conditions of heating burning obtained by product X-ray diffraction analysis（XRD）Figure is respectively referring to attached drawing 1 and attached drawing 2.
Attached drawing 1 is that the present invention prepares silver-colored simple substance coating spinelle type LiMn at different temperatures2O4The XRD diagram of positive electrode Spectrum.It can be seen that by attached drawing 1：The positive electrode of 2% and 10% Ag by weight is coated, in 500 DEG C and 550 DEG C heating 1h of temperature When, their diffraction maximum position does not change, and shows spinel structure（JCPDS 35-0782).In 500 DEG C of condition of temperature Under, when adding in the silver nitrate according to Ag weight meters 2%, there is no Ag in XRD diagram2O dephasigns occur, because of Ag2O content is not up to X- and penetrates less The detection limit of line diffractometer；Under conditions of 500 DEG C of temperature, when adding in the silver nitrate according to Ag weight meters 10%, go out in XRD diagram Existing stronger Ag2O peaks, when showing not add fuel, silver nitrate cannot be converted into elemental silver under this condition；In temperature 550 Under conditions of DEG C, when adding in the silver nitrate according to Ag weight meters 10%, also occurs stronger Ag in XRD diagram2O peaks show not add During refuelling, silver nitrate can not be converted into elemental silver under this condition.
Attached drawing 2 is the present invention in 500 DEG C of temperature（a）With 550 DEG C（b）It is lower to prepare silver-colored simple substance coating spinelle type LiMn2O4Just The XRD spectrum of pole material.Attached drawing 2 is that prepare silver using not same amount glucose under conditions of 500 DEG C of heating temperature with 550 DEG C single Matter coating spinelle type LiMn2O4The XRD diagram of positive electrode.It can be seen from Fig. 2 (a) under conditions of 500 DEG C of temperature, grape Sugared addition less than by weight 15% and it is following when, Ag and LiMn is removed in XRD diagram2O4There is a small amount of Ag outside peak2O peaks, it is impossible to will Silver nitrate is completely converted into elemental silver；Glucose addition by weight 20% and it is above when, only occur in XRD diagram Ag and LiMn2O4Peak, silver nitrate have been completely converted into elemental silver；Fig. 2 (b) is using not same amount Portugal under conditions of 550 DEG C of heating temperature Grape sugar prepares silver-colored simple substance coating spinelle type LiMn2O4The XRD diagram of positive electrode.It can be seen that by Fig. 2 (b)：In heating temperature Under conditions of 550 DEG C, when glucose addition is higher than by weight 5%, only Ag and LiMn in XRD spectrum2O4Peak does not occur Ag2O peaks, only simple substance Ag peaks show that silver nitrate has been completely converted into elemental silver under this condition.
When ignition temperature is 500~600 DEG C, if burning time is less than 1.0h, silver nitrate decomposes incomplete；If combustion The burning time is longer than 1.5h, then causes energy waste, cost raising；Therefore, burning time is reasonable for 1.0~1.5h；It is preferred that Ground is 1.1~1.4h, more preferably 1.2~1.3h.
The invention further relates to the silver-colored simple substance coating spinelle type LiMn that the preparation method is prepared2O4Composite material.
The silver simple substance coating spinelle type LiMn2O4Composite material granular size be 0.2~2.0 μm.
In the present invention, silver-colored simple substance is only coated on LiMn2O4On particle surface, silver content is by weight 2~10%.
The silver-colored simple substance coating spinelle type LiMn being prepared using the method for the present invention2O4Composite material also carried out under State analysis：
I, using conventional scanning electron microscope to silver-colored simple substance coating spinelle type LiMn of the invention2O4Composite material be scanned electricity Sem observation, result is referring to attached drawing 3；
Attached drawing 3 is the silver-colored simple substance coating spinelle type LiMn of the present invention2O4Composite material scanning electron microscope diagram.By attached drawing 3 it is found that present invention silver simple substance coating spinelle type LiMn2O4Composite material reunited by little particle into bulky grain, particle ruler It is very little to be distributed as 0.2~2.0 μm.Overall, the LiMn of cladding204Sample crystal grain corner angle and uncoated variation are little, this It is because the presence of coating does not have an impact grain surface appearance.
II, using classical electrical energy analysis and testing technology to simple substance coating spinelle type LiMn of the invention silver-colored2O4Composite wood Material has carried out charge-discharge performance test, and result is referring to table 1 and attached drawing 4.
The result of table 1 clearly shows, during the material coated with silver, capacity retention ratio is than uncoated LiMn2O4Capacity retention ratio Height, this may be on the one hand silver-colored clad surface modification can reduce contact of the active material with electrolyte, so as to inhibit electrolyte To spinelle LiMn2O4The erosion of material, the Mn that disproportionated reaction on the other hand can be protected to generate2+Ion makes it not to be dissolved into In the middle of electrolyte.Silver is a kind of good conducting medium, it can effectively improve the electric conductivity between electrode material particles, from And improve chemical property.In table 1, LiMn2O4/ Ag first discharge specific capacities are respectively 114.6,118.8,106.8, 100.3 and 95.5mAh/g, after multiplying power 0.5C, 100 cycles, LiMn2O4/ Ag specific discharge capacities are respectively 105.2,107.0, 98.2nd, 91.0 and 86.8mAh/g.The first discharge specific capacity of the material is up to 118.8 mAh/g wherein when silver-colored covering amount is 4%, After 100 charge and discharge cycles, specific discharge capacity still reaches 107.0mAh/g, capacity retention ratio 90.1%, and uncoated LiMn2O4Capacity retention ratio be only 83.6%, hence it is evident that less than material of the present invention.Itself the result shows that, silver cladding be improve conductivity And keep the effective ways of capacity.
Fig. 4 (a) and (b) be respectively in 3.0~4.5 V voltage ranges, LiMn during 0.5 C2O4The constant current of/Ag is put for the first time Electric curve and charge-discharge performance curve.By Fig. 4 (a) it is found that in the range of 3.90~4.25 V, LiMn2O4/ Ag materials are equal There are two apparent discharge platforms for tool, illustrate that lithium ion insertion and deintercalation are carried out in two steps.By Fig. 4 (b) it is found that with Ag Covering amount increase, when silver-colored covering amount be 4% when material first discharge specific capacity than uncoated LiMn2O4First discharge specific capacity is high, This is because the silver added in is a kind of good conducting medium, silver effectively improves the electric conductivity between electrode material particles, from And improve chemical property.Silver is a kind of good conducting medium, and silver effectively improves the conduction between electrode material particles Property, so as to improve chemical property.
Silver simple substance coating spinelle type LiMn of the invention2O4Composite material and preparation method thereof have the characteristics that it is following：
Combustion reaction temperature is low, and the reaction time is short and reaction speed is fast, simple for process, easily realizes industrialized production etc..
Advantageous effect]
The beneficial effects of the invention are as follows：
Compared with prior art, silver is a kind of good conducting medium, and silver effectively improves the conduction between electrode material particles Property, it can add less or be not added with conductive agent when preparing electrode material, so as to improve the chemical property of electrode material.And metal The electric conductivity of oxide cladding is generally poor, when preparing electrode material, to add in carbon black and be added to anode material as conductive agent Material is for forming electrode, and so as to which electrode be made to have relatively good electronic conductivity, but charcoal clandestine meeting reduces the energy dose-effect of lithium battery Rate.
Description of the drawings
Fig. 1 is the present invention silver-colored simple substance coating spinelle type LiMn at different temperatures2O4Composite material XRD analysis figure；
Fig. 2 is the present invention in 500 DEG C of temperature（a）With 550 DEG C（b）It is lower to prepare silver-colored simple substance coating spinelle type LiMn2O4Composite wood The XRD spectrum of material；
Fig. 3 is silver-colored simple substance coating spinelle type LiMn of the invention2O4Composite material scanning electron microscope (SEM) photograph；
a-0%Ag；b-2%Ag；c-5%Ag；d-10%Ag.
Fig. 4 is silver-colored simple substance coating spinelle type LiMn of the invention2O4Composite material first discharge specific capacity and charge and discharge Capacity curve figure.
Specific embodiment
The present invention is will be better understood that by following embodiments.
Embodiment 1：Silver simple substance coating spinelle type LiMn of the invention2O4Composite material preparation.
The embodiment of the embodiment is as follows：
A, silver nitrate solution is prepared
Silver nitrate is dissolved in distilled water, be prepared it is a concentration of by weight 0.8% silver nitrate solution；
B, presoma is prepared
The spinel-type LiMn sold by Beijing Hao Ke Science and Technology Ltd.s with trade name LiMn2O42O4, with glucose according to weight Measure ratio 10：0.8 is uniformly mixed, and is then added to the mixture in the silver nitrate solution that step B is obtained, wherein LiMn2O4With nitre Silver-colored weight ratio 1 in sour silver：0.02,2.2h is stirred with rotating speed 30rpm using blender, makes spinel-type LiMn2O4Dispersion Uniformly, a kind of slurry mix is obtained, then heating 1.0h to evaporate removing moisture, is obtained at 105 DEG C of temperature in drying box Water content is by weight 2.0% presoma；
C, heating burning
The presoma that step B is obtained carries out heating burning 1.0h under conditions of 500 DEG C of air and temperature, and it is single to obtain the silver Matter coating spinelle type LiMn2O4Composite material.
Silver-colored simple substance coating spinelle type LiMn prepared by the embodiment2O4The XRD that is described according to this specification of composite material Analysis determines that particle size distribution is 0.2~2.0 μm with scanning electron microscope analysis, its first discharge specific capacity 114.6mAh/g, 100th specific discharge capacity 105.2mAh/g, capacity retention ratio 91.8%.
Embodiment 2：Silver simple substance coating spinelle type LiMn of the invention2O4Composite material preparation.
The embodiment of the embodiment is as follows：
A, silver nitrate solution is prepared
Silver nitrate is dissolved in distilled water, be prepared it is a concentration of by weight 0.5% silver nitrate solution；
B, presoma is prepared
According to Jintao Liu et al.（Solid State Ionics, 2017, 307:79–89）Point prepared by method is brilliant Stone-type LiMn2O4With glucose according to weight ratio 10：0.5 is uniformly mixed, and the mixture then is added to the nitre that step B obtains In sour silver solution, wherein LiMn2O4With weight ratio 1 silver-colored in silver nitrate：0.10, it is stirred using blender with rotating speed 50rpm 1.8h makes spinel-type LiMn2O4Be uniformly dispersed, obtain a kind of slurry mix, then in drying box at 105 DEG C of temperature plus Hot 2.0h obtains water content as by weight 0.5% presoma to evaporate removing moisture；
C, heating burning
The presoma that step B is obtained carries out heating burning 1.2h under conditions of 600 DEG C of air and temperature, and it is single to obtain the silver Matter coating spinelle type LiMn2O4Composite material.
Silver-colored simple substance coating spinelle type LiMn prepared by the embodiment2O4The XRD that is described according to this specification of composite material Analysis determines that it is reunited by little particle into bulky grain, and particle size distribution is 0.2~2.0 μm with scanning electron microscope analysis, it First discharge specific capacity 95.5mAh/g, the 100th specific discharge capacity 86.8mAh/g and capacity retention ratio 90.9%.
Embodiment 3：Silver simple substance coating spinelle type LiMn of the invention2O4Composite material preparation.
The embodiment of the embodiment is as follows：
A, silver nitrate solution is prepared
Silver nitrate is dissolved in distilled water, be prepared it is a concentration of by weight 1.4% silver nitrate solution；
B, presoma is prepared
The spinel-type LiMn sold by Beijing Hao Ke Science and Technology Ltd.s with trade name LiMn2O42O4With glucose according to weight Than 10：0.6 is uniformly mixed, and is then added to the mixture in the silver nitrate solution that step B is obtained, wherein LiMn2O4With nitric acid Silver-colored weight ratio 1 in silver：0.06,2.0h is stirred with rotating speed 60rpm using blender, makes spinel-type LiMn2O4Dispersion is equal It is even, it obtains a kind of slurry mix, then 1.6 h are heated at 105 DEG C of temperature to evaporate removing moisture in drying box, is contained Presoma of the water for 1.0 % by weight；
C, heating burning
The presoma that step B is obtained carries out heating burning 1.3h under conditions of 540 DEG C of air and temperature, and it is single to obtain the silver Matter coating spinelle type LiMn2O4Composite material.
Silver-colored simple substance coating spinelle type LiMn prepared by the embodiment2O4The XRD that is described according to this specification of composite material Analysis determines that it is reunited by little particle into bulky grain, and particle size distribution is 0.2~2.0 μm with scanning electron microscope analysis, it First discharge specific capacity 106.8mAh/g, the 100th specific discharge capacity 98.2mAh/g and capacity retention ratio 91.9%.
Embodiment 4：Silver simple substance coating spinelle type LiMn of the invention2O4Composite material preparation.
The embodiment of the embodiment is as follows：
A, silver nitrate solution is prepared
Silver nitrate is dissolved in distilled water, be prepared it is a concentration of by weight 2.0% silver nitrate solution；
B, presoma is prepared
The spinel-type LiMn sold by Beijing Hao Ke Science and Technology Ltd.s with trade name LiMn2O42O4With glucose according to weight Than 10：1.0 are uniformly mixed, and are then added to the mixture in the silver nitrate solution that step B is obtained, wherein LiMn2O4With nitric acid Silver-colored weight ratio 1 in silver：0.08,2.2h is stirred with rotating speed 40rpm using blender, makes spinel-type LiMn2O4Dispersion is equal It is even, obtain a kind of slurry mix, then heating 1.4h to evaporate removing moisture, is contained at 100 DEG C of temperature in drying box Water is by weight 1.5% presoma；
C, heating burning
The presoma that step B is obtained carries out heating burning 1.5h under conditions of 560 DEG C of air and temperature, and it is single to obtain the silver Matter coating spinelle type LiMn2O4Composite material.
Silver-colored simple substance coating spinelle type LiMn prepared by the embodiment2O4The XRD that is described according to this specification of composite material Analysis determines that it is reunited by little particle into bulky grain, and particle size distribution is 0.2~2.0 μm with scanning electron microscope analysis, it First discharge specific capacity 100.3mAh/g, the 100th specific discharge capacity 91.0mAh/g and capacity retention ratio 90.7%.
Embodiment 5：Silver simple substance coating spinelle type LiMn of the invention2O4Composite material preparation.
The embodiment of the embodiment is as follows：
A, silver nitrate solution is prepared
Silver nitrate is dissolved in distilled water, be prepared it is a concentration of by weight 1.0% silver nitrate solution；
B, presoma is prepared
According to document Yan Xia et al.（Asian Journal of Chemistry, 2013, 25(4): 1917- 1920）The method of description prepares and through the determining spinel-type LiMn of X-ray diffraction analysis2O4With glucose according to weight ratio 10：0.9 is uniformly mixed, and is then added to the mixture in the silver nitrate solution that step B is obtained, wherein LiMn2O4With silver nitrate The weight ratio 1 of middle silver：0.04,2.0h is stirred with rotating speed 40rpm using blender, makes spinel-type LiMn2O4Dispersion is equal It is even, obtain a kind of slurry mix, then heating 1.8h to evaporate removing moisture, is contained at 105 DEG C of temperature in drying box Water is by weight 0.8% presoma；
C, heating burning
The presoma that step B is obtained carries out heating 1.4 h of burning under conditions of 580 DEG C of air and temperature, obtains the silver Simple substance coating spinelle type LiMn2O4Composite material.
Silver-colored simple substance coating spinelle type LiMn prepared by the embodiment2O4The XRD that is described according to this specification of composite material Analysis determines that it is reunited by little particle into bulky grain, and particle size distribution is 0.2~2.0 μm with scanning electron microscope analysis, it First discharge specific capacity 118.8mAh/g, the 100th specific discharge capacity 107.0mAh/g and capacity retention ratio 90.1%.
Embodiment 6：Silver simple substance coating spinelle type LiMn of the invention2O4Composite material preparation.
The embodiment of the embodiment is as follows：
A, silver nitrate solution is prepared
Silver nitrate is dissolved in distilled water, be prepared it is a concentration of by weight 1.6% silver nitrate solution；
B, presoma is prepared
According to document Wangqiong Xu et al.（International Journal of Electrochemical Science, 2017, 12:9758– 9773）The method of description prepares and through the determining spinel-type of X-ray diffraction analysis LiMn2O4With glucose according to weight ratio 10：0.7 is uniformly mixed, and the mixture then is added to the silver nitrate that step B obtains In solution, wherein LiMn2O4With the weight ratio 1 of silver nitrate：0.09,2.0h is stirred with rotating speed 50rpm using blender, is made Spinel-type LiMn2O4Be uniformly dispersed, obtain a kind of slurry mix, then in drying box at 105 DEG C of temperature heating 1.2h with Evaporation removes moisture, obtains water content as by weight 1.8% presoma；
C, heating burning
The presoma that step B is obtained carries out heating burning 1.3h under conditions of 520 DEG C of air and temperature, and it is single to obtain the silver Matter coating spinelle type LiMn2O4Composite material.
Silver-colored simple substance coating spinelle type LiMn prepared by the embodiment2O4The XRD that is described according to this specification of composite material Analysis determines that it is reunited by little particle into bulky grain, and particle size distribution is 0.2~2.0 μm with scanning electron microscope analysis, it First discharge specific capacity 108.2mAh/g, the 100th specific discharge capacity 100.2mAh/g and capacity retention ratio 92.6%.

Claims (8)

1. a kind of silver simple substance coating spinelle type LiMn2O4Composite material preparation method, it is characterised in that the preparation method Step is as follows：
A, silver nitrate solution is prepared
Silver nitrate is dissolved in distilled water, be prepared it is a concentration of by weight 0.5~2.0% silver nitrate solution；
B, presoma is prepared
Spinel-type LiMn2O4With glucose according to weight ratio 10：0.5~1.0 is uniformly mixed, and is then added to the mixture In the silver nitrate solution that step A is obtained, wherein LiMn2O4It is 1 with weight ratio silver-colored in silver nitrate：0.02~0.10, it is stirred Make spinel-type LiMn2O4It is uniformly dispersed, obtains a kind of slurry mix, then heating evaporation removes moisture, obtains a kind of forerunner Body；
C, heating burning
The presoma obtained in step B is allowed to carry out heating combustion reaction under conditions of 500~600 DEG C of air and temperature, is obtained The silver-colored simple substance coating spinelle type LiMn2O4Composite material.
2. preparation method according to claim 1, it is characterised in that in stepb, using blender with rotating speed 30~ 60rpm is stirred 1.8~2.2h.
3. preparation method according to claim 1, it is characterised in that in stepb, the slurry mix is in drying In case under conditions of 100~105 DEG C of temperature 1.0~2.0h of heat drying.
4. preparation method according to claim 1, it is characterised in that in stepb, the water content of the presoma be with Weight meter 0.5~2.0%.
5. preparation method according to claim 1, it is characterised in that in step C, step B obtains the heating combustion of presoma It is 1.0~1.5h to burn the reaction time.
6. the silver-colored simple substance coating spinelle type being prepared according to preparation method described in any one of claim 1-5 claims LiMn2O4Composite material.
7. silver simple substance coating spinelle type LiMn according to claim 62O4Composite material, it is characterised in that the silver Simple substance coating spinelle type LiMn2O4Composite material granular size be 0.2~2.0 μm.
8. silver simple substance coating spinelle type LiMn according to claim 62O4Composite material, it is characterised in that silver-colored simple substance Only it is coated on LiMn2O4On particle surface, silver content is by weight 2~10%.
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