CN110176595A - A kind of anode material for lithium-ion batteries LiMnO2@C and preparation method thereof - Google Patents

A kind of anode material for lithium-ion batteries LiMnO2@C and preparation method thereof Download PDF

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CN110176595A
CN110176595A CN201910490654.XA CN201910490654A CN110176595A CN 110176595 A CN110176595 A CN 110176595A CN 201910490654 A CN201910490654 A CN 201910490654A CN 110176595 A CN110176595 A CN 110176595A
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lithium
lithium manganate
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CN110176595B (en
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刘兴泉
李�浩
冉淇文
李蕾
郝帅
胡友作
刘金涛
舒小会
张美玲
何泽珍
肖雨
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University of Electronic Science and Technology of China
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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
    • 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
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    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
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Abstract

The invention belongs to field of lithium ion battery, specifically provide a kind of positive electrode laminated cell lithium manganate of lithium ion LiMnO2@C and preparation method thereof, to overcome positive electrode laminated cell lithium manganate of lithium ion (LiMnO2) be difficult to prepare, and the shortcomings that chemical property is poor, phase transition easily occurs for structure and is unable to high-multiplying power discharge.The present invention prepares the MnCO of hexahedron or cube pattern by soft chemical method hydro-thermal reaction3, it is prepared into the Mn of the high activity for identical pattern2O3Low-temperature solid phase reaction is carried out with lithium source afterwards, so that the layered lithium manganate particle prepared is hexahedron or cube structure material, not only crystallinity is high for the material, but also compared with the electrochemical performance under low range；Meanwhile then obtaining the LiMnO that can be discharged under high magnification by carbon coating2@C composite positive pole.

Description

A kind of anode material for lithium-ion batteries LiMnO2@C and preparation method thereof
Technical field
The invention belongs to field of lithium ion battery, are related to anode material for lithium-ion batteries and preparation method thereof, specially one Kind positive electrode laminated cell lithium manganate of lithium ion LiMnO2Preparation method.
Background technique
With the worsening of global environment and weather, energy-saving and emission-reduction are extremely urgent, and countries in the world are also increasingly closed Infuse exploitation and the application in new energy and renewable and clean energy resource.Lithium ion battery as have excellent performance and environmental protection power supply, With energy density height, quickly-chargeable, self discharge it is small, can long-time storage, the superior, memory-less effect of cycle performance etc. it is excellent Point has been widely used for various portable electronics, on electrical equipment, and will become the preferred desired electrical of the following electric car Source.
Batch application is many in the positive electrode of lithium ion battery at present, mainly there is cobalt acid lithium (LiCoO2), lithium nickelate (LiNiO2), lithium manganate having spinel structure (LiMn2O4), nickle cobalt lithium manganate (NCM) and LiFePO 4 (LiFePO4).Wherein, Cobalt acid lithium is the earliest positive electrode for realizing commercial applications, and technology of preparing has developed into ripe so far, and is widely used to On the portable electronic product of compact low power, but being more toxic due to cobalt, scarcity of resources, lead to the manufacture of lithium ion battery At high cost, environmental pollution is big；For lithium nickelate battery due to not overcharging resisting electric discharge, its security performance is worst, overcharges easy on fire, high temperature It is lower to be easy to decompose, keep its thermal stability poor, and poor circulation, commercialization process is centainly hindered；LiFePO 4 Positive electrode is although environment-protecting and non-poisonous, and rich in mineral resources, low raw-material cost, temperature tolerance is splendid, and stable circulation performance is excellent More, but since its electric conductivity is poor, jolt ramming, compacted density are small, and volume is big, and energy density is low and cryogenic property is not good enough, answer it It is restricted with development；Although lithium manganate having spinel structure positive electrode has a safety feature, cryogenic property is preferable, but due to it Theoretical specific capacity it is not high (only 148mAh/g), it is difficult to be made pure phase product, easily occur in cyclic process Jahn-Teller effect It answers, influences the service life of lithium ion battery.Especially under high temperature environment, due to the dissolution of manganese, lithium manganate having spinel structure is followed Ring performance is more unstable.
Although sight has been focused on the higher nickle cobalt lithium manganate of energy density (NCM) and nickel cobalt aluminium both at home and abroad at present On sour lithium (NCA), on especially nickelic NCM811 and NCA815；But both materials result in cost due to scarcity of resources It is higher, and use condition harshness is resulted in and security performance is not good enough since nickel content is very high, in the following pure electric automobile On, the use of these two types of materials is all limited.
With spinel-type LiMn2O4It compares, manganic compound stratiform LiMnO2Improved cycle performance is shown, electricity Press range between 2.0-4.5V, to electrolyte without particular/special requirement；In addition, orthogonal or monoclinic phase stratiform LiMnO2It is a kind of great The rechargeable lithium ion batteries positive electrode of attraction, it is extremely low because it is with height ratio capacity (theoretical specific capacity 285mAh/g) Cost, non-toxic, high-energy density, high environmental acceptability etc., it is considered to be the following low cost high energy density lithium ion electricity The best potential positive electrode in pond.So far, the preparation method of layered lithium manganate is very much, predominantly conventional solid-state method, Lithium source and manganese source are generally respectively Li2CO3、LiOH·H2O、MnO2、MnCO3、Mn2O3, manganese acetate, manganese nitrate, manganese sulfate etc.；Water Thermal method directly produces LiMnO2Although being reported, hydro-thermal method prepares stratiform LiMnO2Method is complex, is not appropriate for industry Change large-scale production；Sol-gel method prepares LiMnO2It is at high cost, and environmental pollution can be brought；And simple solid phase method, it uses High temperature sintering is carried out after grinding or ball milling, although this method simple process, is suitble to commercially produce, particle size distribution Unevenly, it is difficult to prepare the target product of stoichiometric ratio, and chemical property is poor, easily occur during charge and discharge cycles Phase transition of the layer structure to sharp crystal structure.In addition, the layered lithium manganate electric conductivity of pure phase is poor, it is not able to satisfy big multiplying power charge and discharge Electricity causes power density very low, while pure phase stratiform LiMnO2Material will carry out activation by 3-10 charge and discharge cycles Optimal discharge performance can be reached；So needing to probe into out a kind of new material composition and preparing the layer of the composition haveing excellent performance Shape LiMn2O4 (LiMnO2) positive electrode method.
Summary of the invention
It is an object of the invention to be directed to positive electrode laminated cell lithium manganate of lithium ion (LiMnO2) be difficult to prepare, and electricity The shortcomings that chemical property is poor, phase transition easily occurs for structure, provides a kind of positive electrode laminated cell lithium manganate of lithium ion (LiMnO2) preparation method, this method combination hydro-thermal method synthesizes high activity presoma and low-temperature solid-phase method and synthesizes nanostructured layers Shape LiMnO2.The anode material for lithium-ion batteries LiMnO that the present invention synthesizes2Specific discharge capacity with higher and excellent circulation Stability, carbon-coated layered lithium manganate LiMnO2@C can satisfy high-energy density, high power density and big multiplying power charge and discharge Electricity demanding, preparation method overcome that simple solid-phase synthesis particle size is unevenly distributed and chemical property difference etc. lacks Point, the product purity of preparation is high, chemical uniformity is good, crystalline quality is high, product grain is tiny and is evenly distributed, chemical property Excellent and manufacturing cost is lower；The phase transition from layer structure to cubic spinel structure will not occur in charge and discharge process, Cycle performance is splendid.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of anode material for lithium-ion batteries LiMnO2@C, which is characterized in that the anode material for lithium-ion batteries LiMnO2@C is that carbon (C) coats layered lithium manganate (LiMnO2) composite material, wherein carbon (C) covering amount is 0.5~2.0wt%； The composite material crystal structure has dotted coating in the hexahedron pattern and surface of rule, and hexahedral maximal side is 8 A length of 1~the 2um of~10um, minimum edge, soilless sticking phenomenon.
Even, the composite material crystal structure is in cube pattern.
Above-mentioned anode material for lithium-ion batteries LiMnO2The preparation method of@C, comprising the following steps:
Manganese nitrate is added in deionized water step 1., is stirred at room temperature and makes it completely dissolved, obtains manganese nitrate concentration For the solution A of 1.0mol/L；
Urea is added in deionized water step 2., is stirred at room temperature and makes it completely dissolved, obtaining urea concentration is The solution B of 4.0mol/L；
Ammonium fluoride is added in deionized water step 3., is stirred at room temperature and makes it completely dissolved, and obtains fluorination ammonium concentration For the solution C of 2.0mol/L；
Step 4. stirs to get mixed together with steps 1 and 2,3 acquired solution A, B and C are added with the speed of 10ml/min Solution is closed, and constantly stirs to get mixing suspension, wherein solution A, B and C are isometric mixing；
The obtained suspension of step 4 is transferred in autoclave by step 5., loading 80%, sealing autoclave； 5~12h of hydro-thermal reaction, obtains MnCO at 180 DEG C3Crystal settling；
Step 5 gained white crystal precipitated product is placed in air dry oven by step 6., dry at 80~120 DEG C 5~8h obtains MnCO3Powder；
Step 7. is by the resulting MnCO of step 63Powder is placed in Muffle furnace, 450~650 DEG C of thermal decompositions 5 in air ~20h obtains Mn2O3Powder；
Step 8. is according to molar ratio Li+/Mn3+=1.05~1.25 weigh LiOH or Li2CO3It is obtained with step 7 Mn2O3Powder is uniformly mixed, and obtains mixture of powders；
The obtained mixture of powders of step 8 is placed in ceramic boat by step 9., is placed in tube furnace, in argon atmosphere Under in 650~900 DEG C be sintered 10~for 24 hours to get arrive layered lithium manganate target product；
The obtained target product of step 9 is added in sucrose solution and stirs evenly by step 10., dry；Then in nitrogen Gas or the lower 500 DEG C of 2~5h of thermal decomposition of argon atmosphere are to get arriving final product carbon coating layered lithium manganate LiMnO2@C composite wood Material.Gained carbon coating layered lithium manganate LiMnO2@C composite still shows the hexahedron even cube pattern of rule, table There are many dotted coating, hexahedral maximal side is 8~10um, a length of 1~2um of minimum edge, without agglomeration in face.Material After material insertion lithium ion, the grain diameter and pattern of material still maintain presoma manganese carbonate and Mn2O3Particle size and shape Looks.
The present invention prepares the MnCO of hexahedron or cube pattern by soft chemical method hydro-thermal reaction3, it is prepared into For the Mn of the high activity of identical pattern2O3Low-temperature solid phase reaction is carried out with lithium source afterwards, so that the layered lithium manganate particle prepared is Hexahedron or cube structure material, grain crystalline degree is high, and compared with the electrochemical performance under low range；Pass through carbon again Cladding obtains the LiMnO that can be discharged under high magnification2@C composite positive pole.
In conclusion the present invention has the advantage that
1, the present invention learns the technique that hydro-thermal method is combined with low-temperature solid-phase method using softening, prepares six by liquid phase reactor The precursor powder of face body or cube pattern, then the micron-sized stratiform for preparing identical pattern is sintered by low-temperature solid-phase method Lithium manganate particle obtains the LiMnO of hexahedron or cube pattern finally by carbon coating2@C composite positive pole.This method The shortcomings that overcoming conventional solid synthetic method, the product crystalline quality of preparation is excellent, chemical uniformity is good, particle is tiny, purity It is high, can high current high-multiplying power discharge.
2, positive electrode laminated cell lithium manganate of lithium ion prepared by the present invention specific discharge capacity with higher and excellent Stable circulation performance, be suitable for high energy density cells charge-discharge power demand；Under room temperature environment, when constant current charge-discharge multiplying power When for 0.1C, the first discharge specific capacity of the layered lithium manganate positive electrode can reach 216mAh/g, after circulation 50 times still It can reach 206mAh/g, capacity retention ratio is up to 95.4%.Carbon-coated layered lithium manganate LiMnO2@C positive electrode material can be Higher specific discharge capacity and cycle performance are obtained under 0.5C multiplying power.
3, reaction raw material used are all general chemical products in technique of the invention, and raw material sources are abundant, cheap, Manufacturing cost is extremely low.Carbon source is ordinary food grade cane sugar or glucose.
4, device therefor is simpler in technique of the invention, generates, had both met green without poisonous and harmful substance in preparation process Colour circle protects concept, and is easily achieved scale industrial production.
Detailed description of the invention
Fig. 1 is that the present invention prepares anode material for lithium-ion batteries LiMnO2Process flow chart.
Fig. 2 is that the present invention prepares anode material for lithium-ion batteries LiMnO2The process flow chart of@C.
Fig. 3 is that the present invention prepares anode material for lithium-ion batteries LiMnO2XRD diagram.
Fig. 4 is that the present invention prepares precursor of lithium ionic cell positive material MnCO3(left side) and LiMnO2The SEM of@C (right side) schemes.
Fig. 5 is that the present invention prepares anode material for lithium-ion batteries LiMnO2First charge-discharge curve under 0.1C multiplying power Figure.
Fig. 6 is that the present invention prepares anode material for lithium-ion batteries LiMnO2The tenth charging and discharging curve under 0.1C multiplying power Figure.
Fig. 7 is that the present invention prepares anode material for lithium-ion batteries LiMnO2Cycle performance curve graph under 0.1C multiplying power.
Fig. 8 is that the present invention prepares anode material for lithium-ion batteries LiMnO2Cycle performance curve of the@C under 0.5C multiplying power Figure.
Specific embodiment
The present invention is described in further detail with attached drawing combined with specific embodiments below.
Embodiment 1
0.1mol manganese nitrate is added in 100ml deionized water and is configured to solution A, 0.4mol urea addition 100ml is gone It is configured to solution B in ionized water, 0.2mol ammonium fluoride is added in 100ml deionized water and is configured to solution C, then under stiring In being transferred to after solution A, solution B and solution C are stirred for uniformly so that in the speed addition beaker of 10ml/min, addition is finished simultaneously In the stainless steel autoclave of lining teflon, loading 80% seals autoclave, the hydro-thermal reaction at 180 DEG C 5h, centrifuge separation are precipitated respectively three times with deionized water and dehydrated alcohol cross washing, obtain MnCO3White crystal precipitating；It will MnCO3White crystal precipitated product is placed in air dry oven, and dry 4h obtains MnCO at 90 DEG C3White powder；By MnCO3 White powder is placed in Muffle furnace 450 DEG C of thermal decomposition 2h in air atmosphere, obtains Mn2O3Precursor powder.By presoma Mn2O3 And LiOHH2O mixed grinding is uniform, then 650 DEG C of low-temperature sintering 12h under protection of argon gas, obtains layered lithium manganate anode material Expect LiMnO2；As shown in Figure 1；
By LiMnO obtained2Positive electrode is added in the sucrose solution that concentration is 20%, keeps LiMnO2In positive electrode Carbon content between 0.5-2.0wt%, stir, dry, then under high-purity argon gas atmosphere 500 DEG C thermal decomposition 3h is ground up, sieved to get LiMnO is arrived after cooling2@C composite positive pole；As shown in Figure 2.
It is illustrated in figure 3 uncoated anode material for lithium-ion batteries LiMnO prepared by the present invention2XRD diagram, can from Fig. 3 To find out, material is orthogonal type LiMnO2Feature XRD diffraction spectra, diffraction maximum and standard spectrogram are completely coincident unanimously.
As Fig. 4 (left side) show presoma MnCO3Electron scanning micrograph, as can be seen that forerunner from left figure Body MnCO3The hexahedron even cube pattern of rule is showed, there are many dotted coating, hexahedral maximal sides on surface For 8~10um, a length of 1~2um of minimum edge, without agglomeration.After material is embedded in lithium ion, the grain diameter and pattern of material Still maintain presoma manganese carbonate and Mn2O3Particle size and pattern, as shown in Fig. 4 (right side).
To the anode material for lithium-ion batteries LiMnO of preparation2Constant current charge-discharge test is carried out, it can from test result Positive electrode specific discharge capacity with higher and excellent stable circulation performance out；Under room temperature environment, when constant current fills When discharge-rate is 0.1C, the first discharge specific capacity of the layered lithium manganate anode material for lithium-ion batteries can reach 155mAh/g (Fig. 5), the specific discharge capacity that circulation is the 10th time is up to 216mAh/g (Fig. 6), and specific discharge capacity is still reachable after recycling 50 times To 206mAh/g or more (Fig. 7), capacity retention ratio is up to 95.4%.Similarly, to the anode material for lithium-ion batteries of preparation LiMnO2@C carries out constant current charge-discharge test, from test result it can be seen that positive electrode multiplying power discharging ratio with higher Capacity and excellent stable circulation performance.Under room temperature environment, when constant current charge-discharge multiplying power is 0.5C, carbon coating Layered Manganese Sour lithium ion battery positive electrode LiMnO2The first discharge specific capacity of@C can reach 206.3mAh/g, the 2nd electric discharge ratio Capacity is up to 223.2mAh/g, and specific discharge capacity still can reach 216.9mAh/g or more, capacity retention ratio after recycling 50 times Up to 97.2% (Fig. 8).
Comparative example 1
Weigh analytically pure chemical reagent 0.005mol Mn2O3With the LiOHH of 0.011mol2O mixed grinding is uniform, so 650 DEG C of sintering 12h under protection of argon gas afterwards, obtain layered lithium manganate positive electrode LiMnO2.Then to the lithium-ion electric of preparation Pond layered lithium manganate LiMnO2Positive electrode carries out constant current charge-discharge test, from test result it can be seen that the positive electrode Specific discharge capacity and stable circulation performance are poor；Under room temperature environment, when constant current charge-discharge multiplying power is 0.1C, the stratiform First discharge specific capacity after manganate lithium ion battery positive electrode activates completely is only 103.3mAh/g, highest electric discharge ratio Capacity is up to 105.8mAh/g, and specific discharge capacity is only 80.2mAh/g, capacity retention ratio 77.6% after recycling 50 times.
Comparative example 2
Weigh 0.1mol white powder MnCO3Pure chemistry reagent is analyzed, by MnCO3White powder is placed in air in Muffle furnace 450 DEG C of thermal decomposition 2h, obtain Mn in atmosphere2O3Powder, then the 0.005mol Mn weighed2O3With the LiOH of 0.011mol H2O mixed grinding is uniform, then 650 DEG C of sintering 12h under protection of argon gas, obtains layered lithium manganate positive electrode LiMnO2.Then To the lithium ion battery stratiform LiMn2O4 LiMnO of preparation2Positive electrode carries out constant current charge-discharge test, can be with from test result Find out that specific discharge capacity and the stable circulation performance of the positive electrode are still poor；Under room temperature environment, when constant current charge-discharge times When rate is 0.1C, the first discharge specific capacity after which activates completely is only 121.6mAh/g, highest specific discharge capacity is up to 123.1mAh/g, and specific discharge capacity is only 101.3mAh/g after recycling 50 times, Capacity retention ratio is 83.3%.
By the above comparative example 1 with comparative example 2 it is found that either directlying adopt technical grade MnCO3It is prepared into Mn2O3Powder, Still technical grade Mn is directlyed adopt2O3Powder and LiOHH2The layered lithium manganate LiMnO that O mixed sintering obtains2Electrochemistry It can be all well below the present invention, it can be seen that, hexahedron is strictly only prepared into using present invention process process and technological parameter Or the MnCO of cube pattern3Powder, and it is made into the Mn of the high activity for identical pattern2O3It is anti-that solid phase is carried out with lithium source afterwards It answers, is prepared into layered lithium manganate LiMnO2Can just have the excellent chemical property of the present invention；Being obtained again by carbon coating can be high The LiMnO of multiplying power discharging2@C composite positive pole.
The above description is merely a specific embodiment, any feature disclosed in this specification, except non-specifically Narration, can be replaced by other alternative features that are equivalent or have similar purpose；Disclosed all features or all sides Method or in the process the step of, other than mutually exclusive feature and/or step, can be combined in any way.

Claims (2)

1. a kind of anode material for lithium-ion batteries LiMnO2@C, which is characterized in that the anode material for lithium-ion batteries LiMnO2@C Layered lithium manganate (LiMnO is coated for carbon (C)2) composite material, wherein carbon (C) covering amount is 0.5~2.0wt%；It is described compound Material crystal structure has a dotted coating in the hexahedron pattern and surface of rule, hexahedral maximal side be 8~10um, A length of 1~the 2um of minimum edge, soilless sticking phenomenon.
2. a kind of anode material for lithium-ion batteries LiMnO2The preparation method of@C, comprising the following steps:
Manganese nitrate is added in deionized water step 1., is stirred at room temperature and makes it completely dissolved, obtaining manganese nitrate concentration is The solution A of 1.0mol/L；
Urea is added in deionized water step 2., is stirred at room temperature and makes it completely dissolved, and obtaining urea concentration is 4.0mol/ The solution B of L；
Ammonium fluoride is added in deionized water step 3., is stirred at room temperature and makes it completely dissolved, and obtains fluorination ammonium concentration and is The solution C of 2.0mol/L；
It is molten to stir to get mixing together with steps 1 and 2,3 acquired solution A, B and C are added with the speed of 10ml/min for step 4. Liquid, and constantly stir to get mixing suspension, wherein solution A, B and C are isometric mixing；
The obtained suspension of step 4 is transferred in autoclave by step 5., loading 80%, sealing autoclave；Then at 5~12h of hydro-thermal reaction, obtains MnCO at 180 DEG C3Crystal settling；
Step 5 gained white crystal precipitated product is placed in air dry oven by step 6., dry 5 at 80~120 DEG C~ 8h obtains MnCO3Powder；
Step 7. is by the resulting MnCO of step 63Powder is placed in Muffle furnace, 450~650 DEG C of 5~20h of thermal decomposition in air Obtain Mn2O3Powder；
Step 8. is according to molar ratio Li+/Mn3+=1.05~1.25 weigh LiOH or Li2CO3With the obtained Mn of step 72O3Powder It is uniformly mixed, obtains mixture of powders；
The obtained mixture of powders of step 8 is placed in ceramic boat by step 9., is placed in tube furnace, under an argon atmosphere in 650~900 DEG C of sintering 10~for 24 hours, obtain layered lithium manganate target product；
The obtained target product of step 9 is added in sucrose solution and stirs evenly by step 10., dry；Then in nitrogen or The lower 500 DEG C of 2~5h of thermal decomposition of argon atmosphere to get arrive final product carbon coating layered lithium manganate LiMnO2@C composite.
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