CN107910529A - A kind of ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding and preparation method thereof - Google Patents
A kind of ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding and preparation method thereof Download PDFInfo
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- CN107910529A CN107910529A CN201711149758.1A CN201711149758A CN107910529A CN 107910529 A CN107910529 A CN 107910529A CN 201711149758 A CN201711149758 A CN 201711149758A CN 107910529 A CN107910529 A CN 107910529A
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- 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
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a kind of ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding, utilize the self assembly performance of MOFs materials, cladding to spherical ternary cathode material is realized by simple one-step method, with layer structure, there is no impurities phase presence, cladding does not cause the structure of material to change, and has the two level near-spherical structure formed by the bar-shaped little particle aggregation of piece.Its preparation method includes：1）The preparation of presoma；2）The preparation of spherical ternary cathode material；3）The preparation of the tertiary cathode material of manganese Base Metal organic frame compound cladding.As the application of cell positive material, after 0.5 C constant current charge-discharges 50 circle, specific discharge capacity is 160 ~ 180 mAh g‑1, under 10 C high magnifications, specific discharge capacity is 140 ~ 160 mAh g‑1.The present invention has the following advantages：Porous channel is provided, improves infiltration degree, improves cyclical stability and big circulation performance；Strengthen the stability of M O bond energys；Cost is low, easy to operate, can be suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of NEW TYPE OF COMPOSITE porous material, is specially a kind of manganese Base Metal organic frame compound cladding
Ternary cathode material of lithium ion battery and preparation method thereof.
Background technology
With energy shortage and being on the rise the problems such as environmental pollution, sustainable novel energy is cleaned in exploitation to be become
The emphasis of whole world scientist concern.As the important component in lithium ion battery --- positive electrode, its operating voltage
Globality of the performances such as scope, long-term cycle life, charge/discharge capacity height, security and stability quality to whole lithium ion battery
Decisive role can be played, becomes one of crucial conditionality factor for determining performance of lithium ion battery.[Solid State
Ionics 2012, 221, 1-5]
The positive electrode currently received significant attention mainly includes the LMO of layer structure2（M=Co, Ni, Mn etc.）, novel lamellar
LiNi1-x-yCoxMnyO2, new lithium-rich Li1+xNi1-y-zMnyCozO2, spinel structure LiMn2O4（LiMn2O4）, olive
The LiMPO of stone structure4（M=Fe, Mn, Co etc.）And other kinds of positive electrode（Oxyvanadium compound, ferric flouride）Etc..And
Wherein, the positive electrode LiNi of stratiformxCoyMnzO2(x+y+z=1) is due to stable structure, security is good, cost is low and has higher
Capacity, the advantages that energy density is high, it is considered to be most possibly substitute LiCoO2Positive electrode, especially LiNi1/3Co1/ 3Mn1/3O2, have and LiCoO2The same a-NaFeO2Type layer structure, but also with obvious Ni-Co-Mn synergistic effects：
Ni elements are main active materials, using the teaching of the invention it is possible to provide the reversible capacity of higher；Co elements are capable of the layer structure of stabilizing material simultaneously
Suppress cation mixing, improve the electric conductivity and cyclical stability of positive electrode；Mn elements can effectively improve the peace of material
Full performance simultaneously reduces cost, therefore tertiary cathode material becomes most one of anode material of lithium battery of prospect, particularly suitable for
Lithium ion battery used for electric vehicle.But following under the high rate charge-discharge performance of this material and high charge blanking voltage
Ring stability still has much room for improvement.Therefore, new preparation method is explored, material is doped and coating modification, further
The tap density and chemical property of raising positive electrode are still research hotspot from now on.In the prior art, it is commonly used and mixes
Cladding means improve the security and stability of lithium ion battery, as disclosed in the patent 107039650A《A kind of manganese coating modification lithium
Battery tertiary cathode material and preparation method thereof》, but this cladding means preparation process is complicated, and manufacturing cost is higher, improves
But the specific discharge capacity of material is reduced while security and stability.[Chem. Mater. 2017, 29, 3883-3890]
Metal organic framework compound（MOFs）As a kind of new hybrid inorganic-organic materials, it is subject in recent years extensive
Concern.MOFs is the unlimited lattice that is formed by metal ion or ion cluster and organic ligand by the form of self assembly.Exactly
Due to its unique property, for example, stable nano pore, high-specific surface area, homogeneous and adjustable aperture, feature duct,
Can surface be modified etc. outstanding properties, determine its gas storage, catalysis, sensing and detaching direction possess numerous applications.Therefore,
The self assembly characteristic that MOFs possesses, makes it present big advantage and potential application in terms of sample surfaces modification.[J.
Am. Chem. Sc. 2017, 139, 4753-4761]。
The content of the invention
The object of the present invention is to provide a kind of lithium ion battery tertiary cathode of manganese Base Metal organic frame compound cladding
Material and preparation method thereof.
The stable circulation under high rate charge-discharge performance and high charge blanking voltage for existing tertiary cathode material
The shortcomings of property is poor, carries out it using metal organic framework compound surface cladding, it is therefore an objective to do not reducing material discharging specific volume
On the premise of amount, the cyclical stability of material and big high rate performance are improved.
To achieve the above object, the technical solution adopted by the present invention is：
The ternary cathode material of lithium ion battery of a kind of manganese Base Metal organic frame compound cladding, using MOFs materials from group
Performance is filled, the cladding to spherical ternary cathode material is realized by simple one-step method, there is layer structure, no impurities phase is deposited
Coating and do not causing the structure of material to change, there is the two level near-spherical structure formed by the bar-shaped little particle aggregation of piece.
The preparation method of the ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding includes following
Step：
Step 1）The preparation of presoma, configures certain density nickel, cobalt, manganese Metal mixed salt solution, while configures a certain concentration
Carbonate solution as precipitating reagent, under protective atmosphere, above two solution is distinguished by peristaltic pump with certain speed
Constantly it is pumped into reactor, at the same time, suitable ammonia spirit is added dropwise and adjusts pH；In reaction process, precise control of temperature,
PH and mixing speed, ageing a period of time after reaction, by the product after above-mentioned ageing, by filtering, washing, in certain bar
Under part presoma is obtained after drying；The lithium source is Li2CO3Or LiOHH2O, metal salt are sulfate or acetate, precipitating reagent
For sodium carbonate or ammonium hydrogen carbonate, in reaction process, temperature control is at 45 ~ 80 DEG C, and 7.5 ~ 9, mixing speed control exists for pH controls
800 ~ 1200 rpm/min, after reaction digestion time control use deionized water in 10 ~ 18 h, washing process, and vacuum is done
Dry condition is that 12 ~ 24 h are kept at 50 ~ 80 DEG C；
Step 2）The preparation of spherical ternary cathode material, by step 1）The presoma, with certain chemical dosage ratio, claims with lithium source
Take presoma and Li2CO3After ground and mixed is uniform, calcine under certain condition, spherical tertiary cathode material is made after natural cooling
The chemical dosage ratio of material, the presoma and lithium source is 1：1.05 ~ 1.10, calcining heat is 800 ~ 900 DEG C；
Step 3）The preparation of the tertiary cathode material of manganese Base Metal organic frame compound cladding, with metal manganese salt, organic carboxyl acid
With spherical anode material with the ratio between amount of material for metal manganese salt：Organic carboxyl acid：Tertiary cathode material=2:1:（100~400）, will
Metal manganese salt is dissolved in solvent with organic carboxyl acid, and adds step 2）Gained spherical ternary cathode material, stirs certain time
Afterwards, reaction kettle is enclosed, carries out hydro-thermal reaction, by above-mentioned hydro-thermal reaction product, by filtering, washing, drying under certain condition
Afterwards, be made the ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding, the manganese salt for manganese acetate or
Manganese chloride, organic carboxyl acid are 2,5-Dihydroxyterephthalic acid, solvent DMF, ethanol and deionized water, the hydro-thermal reaction bar
Part is 70-120 DEG C, and the reaction time is 2-6 h, the step 3）Filtering and washing process in using organic solvent carry out it is more
Secondary washing, the step 3）Drying condition be 50 ~ 80 DEG C be dried in vacuo 12 ~ 24 h after, in 160 ~ 250 DEG C of forced air dryings
6~12 h。
The ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding is as cell positive material
Using after 0.5 C constant current charge-discharges 50 circle, specific discharge capacity is 160 ~ 180 mAh g-1, under 10 C high magnifications, electric discharge
Specific capacity is 140 ~ 160 mAh g-1。
In order to verify the remarkable effect of manganese Base Metal organic frame compound cladding, according to above-mentioned manganese Base Metal organic frame
The preparation method that the tertiary cathode material of compound cladding is identical is prepared for uncoated tertiary cathode material, not specified
Step is identical with above-mentioned preparation method, and difference is：Not comprising the step 3）.
The advantageous effects that the present invention possesses are confirmed by following experiment.
Electrochemical property test：To tertiary cathode material uncoated made from embodiment and manganese Base Metal organic frame
The chemical property of the tertiary cathode material of compound cladding is tested, and detailed process is as follows：The test of chemical property uses
CR2025 batteries, using NMP as solvent, the tertiary cathode that manganese Base Metal organic frame compound made from embodiment is coated
Material and uncoated tertiary cathode material and acetylene black and Kynoar are with mass ratio 8:1:1 ground and mixed, afterwards will be equal
Homogenate material is applied on aluminium foil, and is placed at 110 DEG C and is dried in vacuum overnight, and the load capacity of electrode slice is controlled 0.5 ~ 2.0
mg cm-2；Electrolyte is by a certain amount of l mol/L LiPF6Volume ratio is dissolved in as 1:In the mixed solution of 1 EC and DEC；
Using celgard as membrane, pure lithium is used as to electrode；Glove box (the H being assembled in full of argon gas atmosphere of related battery2O,
O2：<1 ppm) in carry out；The constant current charge-discharge test of battery carries out charge and discharge on Neware BTS3000 battery test systems
Electrical testing, test environment maintain 25 DEG C of constant temperature, and the voltage range of test is 2.5 ~ 4.5 V.
The XRD of uncoated tertiary cathode material and the tertiary cathode material of manganese Base Metal organic frame compound cladding is surveyed
Test result shows that the diffraction maximum of two kinds of materials is all very sharp, diffraction maximum and stratiform α-NaFeO2Structure, diffraction maximum is consistent, explanation
Material crystalline prepared by coprecipitation method is fine, exists without obvious impurities phase；Diffraction maximum (006)/(102) and (108)/
(110) obvious division occurs, illustrates that material all has good layer structure, while also indicates that cladding does not cause material
Structure changes.
The SEM of uncoated tertiary cathode material and the tertiary cathode material of manganese Base Metal organic frame compound cladding is surveyed
Test result shows that material prepared by coprecipitation method shows the two level near-spherical structure formed by the bar-shaped little particle aggregation of piece,
The pattern of material is not changed after manganese Base Metal organic frame compound cladding.
TEM the and HR-TEM test results of tertiary cathode material of manganese Base Metal organic frame compound cladding show, ball
The surface of shape tertiary cathode material has successfully coated manganese Base Metal organic frame compound.
The tertiary cathode material that uncoated tertiary cathode material is coated with manganese Base Metal organic frame compound is in 0.5 C
Loop test under current density the result shows that, uncoated 180 ~ 190 mAh g of tertiary cathode material first discharge specific capacity-1,
During constant current charge-discharge, capacity is gradually decayed, and capacity attenuation is to 120 ~ 130 mAh g after 50 circle circulations-1.And after coating
Material discharging specific capacity be promoted to（Improve 15 ~ 30%）, cyclical stability（Improve 10 ~ 20%）And capacity retention ratio（Raising 10 ~
30%）There is significant raising than uncoated tertiary cathode material, capacity remains at 175 ~ 180 mAh after 50 circle circulations
g-1。
The tertiary cathode material that uncoated tertiary cathode material is coated with manganese Base Metal organic frame compound is in difference
High rate performance test result under current density shows, the mA g of 1 C=200-1, charge-discharge test follows under 0.5 C current densities
Ring 5 encloses, and specific discharge capacity is 170 ~ 180 mAh g-1；Charge-discharge test circulation 5 is enclosed under 1 C current densities, specific discharge capacity
160~170 mAh g-1；Charge-discharge test circulation 5 is enclosed under 2 C current densities, 140 ~ 150 mAh g of specific discharge capacity-1；5
Charge-discharge test circulation 5 is enclosed under C current densities, 130 ~ 140 mAh g of specific discharge capacity-1；The discharge and recharge under 10 C current densities
Test loop 5 is enclosed, 120 ~ 130 mAh g of specific discharge capacity-1；When current density is again lowered to 1 C and the small electricity of 0.5 C from 10 C
Under current density during charge-discharge test circulation, specific discharge capacity gos up to 140 ~ 150 mAh g-1, but less than low current density first
Specific discharge capacity under charge and discharge cycles state.And the tertiary cathode material circulation of manganese Base Metal organic frame compound cladding is steady
It is qualitative（Improve 5 ~ 10%）And high rate capability（Improve 10 ~ 30%）It is enhanced than uncoated tertiary cathode material,
Under 10 C, remain to be maintained at 150 ~ 160 mAh g-1High specific discharge capacity, and after high current density circulates
Low current density discharge and recharge remains to keep high specific discharge capacity.
The ternary cathode material of lithium ion battery of above-mentioned a kind of manganese Base Metal organic frame compound cladding, compared to existing
Coating technology, the obvious advantage that technical solution of the present invention has is：
1st, make material that there is excellent chemical property by cladding means, metal organic framework compound carries out surface cladding
Afterwards, porous channel is provided for material, adds the specific surface area of material, improve the infiltration degree of material and electrolyte, there is provided
More lithium ion diffusion admittances, while relatively thin SEI films are formed, improve the cyclical stability of material and big circulation
Energy；
2nd, manganese Base Metal organic frame compound, which not only has in Adlattice, discharges O2Effect, strengthen M-O bond energys（M=Ni、
Co、Mn）Stability；
3rd, the manganese in manganese Base Metal organic frame compound take part in electrochemical reaction, improve material circulation stability and use
Specific capacity is also lifted while service life；
4th, tertiary cathode material is prepared by co-precipitation, then manganese Base Metal organic frame compound cladding is prepared with hydro-thermal method
Ternary cathode material of lithium ion battery, this method has the advantages that cost is low, operation is simple and safe and pollution-free, energy
It is enough to be suitable for large-scale production.
The ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding prepared by this method, avoids passing
Size and pattern of the cladding means of uniting there are equipment complex and expensive, by institute's coating decoration matrix are limited and encapsulation steps are multistage
It is cumbersome, the shortcomings of but greatly reducing specific capacity while cyclical stability improves.The cladding means utilize oneself of MOFs materials
Assembling property, the cladding of material is realized by simple one-step method, and preparation process is simple, saves energy consumption, manufacturing cost
It is low, and chemical property is obviously improved, and is obviously improved in cyclical stability, specific capacity, high rate performance etc., this method
Have a wide range of applications, be expected into and promote the use of.
Brief description of the drawings
Fig. 1 is the uncoated tertiary cathode material and manganese Base Metal organic frame compound cladding prepared in embodiment
The XRD diagram of ternary cathode material of lithium ion battery；
Fig. 2 be the uncoated tertiary cathode material for preparing and manganese Base Metal organic frame compound cladding in embodiment lithium from
The SEM figures of sub- battery tertiary cathode material；
Fig. 3 is the ternary cathode material of lithium ion battery of the manganese Base Metal organic frame compound cladding prepared in embodiment
TEM and HR-TEM figures；
Fig. 4 be the uncoated tertiary cathode material for preparing and manganese Base Metal organic frame compound cladding in embodiment lithium from
Cycle performance figure of the sub- battery tertiary cathode material under 0.5 C current densities, the mA g of 1 C=200-1；
Fig. 5 is the uncoated tertiary cathode material and the ternary of manganese Base Metal organic frame compound cladding prepared in embodiment
High rate performance figure of the positive electrode under different current densities, 0.5 C-1 C-2 C-5 C-10 C-1 C-0.5 C, 1 C=200
mA g-1。
Embodiment
The present invention is described in further detail present invention with reference to Figure of description, but be not pair by embodiment
The restriction of the present invention.
Embodiment
A kind of preparation method of the ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding, gained
Material abbreviations are Mn-MOF coated NCM：
Step 1）The preparation of presoma, accurately weighs the nickel sulfate of 2.6821 g, the cobaltous sulfate of 2.8394g, the sulphur of 1.7073 g
Sour manganese dissolves in 200 mL deionized waters and is mixed into solution, while weighs 3.1930 g sodium carbonate and be dissolved in 200 mL deionized waters and be made
Solution, in N2Under protective atmosphere, above two solution is constantly pumped into reactor respectively by peristaltic pump（Five mouthfuls of flasks）In,
At the same time, it is 8.5 that ammonia spirit, which is added dropwise, and adjusts pH, under the conditions of 50 DEG C, is carried out using mixing speed as 1000 rpm/min anti-
Should, 12 h are aged after reaction, product is filtered, and are repeatedly washed with deionized water, then under the conditions of 80 DEG C, vacuum drying
12 h, obtain presoma；
Step 2）The preparation of spherical ternary cathode material, by step 1）The presoma and lithium source chemical dosage ratio 1：1.05 claim
Take 6.9770 g presomas and 1.1756 g Li2CO3After ground and mixed is uniform, 450 are warming up to by 3 DEG C/min of heating rate
DEG C calcining, after keeping 5 h, then is warming up to 850 DEG C of 12 h of holding, spherical ternary cathode material is made after natural cooling；
Step 3）The preparation of the ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding, by 0.0955 g
Manganese acetate and the 2,5- dihydric para-phthalic acids of 0.0386 g be dissolved in the DMF of 45 mL, the absolute ethyl alcohol of 3 mL and 3
In the organic solvent mixed solution of the deionized water composition of mL, and add 2.0 g steps 2）Gained spherical ternary cathode material, magnetic
After power stirs 30 min, reaction kettle is enclosed, 2 h of hydro-thermal reaction at 120 DEG C, more product filtering, DMF washings after completion of the reaction
Afterwards, under the conditions of 50 DEG C, 12 h is dried in vacuo, place into air dry oven, dry 5 h are removed organic under the conditions of 200 DEG C
Solvent, is made the ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding.
In order to verify the remarkable effect of manganese Base Metal organic frame compound cladding, according to above-mentioned manganese Base Metal organic frame
The preparation method that the tertiary cathode material of compound cladding is identical is prepared for uncoated tertiary cathode material, its chemical formula is
LiNi1/3Co1/3Mn1/3O2, NCM is abbreviated as, not specified step is identical with above-mentioned preparation method, and difference is：No
Include the step 3）.
Electrochemical property test：To tertiary cathode material uncoated made from embodiment and manganese Base Metal organic frame
The chemical property of the tertiary cathode material of compound cladding is tested, and detailed process is as follows：The test of chemical property uses
CR2025 batteries, using NMP as solvent, the tertiary cathode that manganese Base Metal organic frame compound made from embodiment is coated
Material and uncoated tertiary cathode material and acetylene black and Kynoar are with mass ratio 8:1:1 ground and mixed, afterwards will be equal
Homogenate material is applied on aluminium foil, and is placed at 110 DEG C and is dried in vacuum overnight, and the load capacity of electrode slice is controlled 0.5 ~ 2.0
mg cm-2；Electrolyte is by a certain amount of l mol/L LiPF6Volume ratio is dissolved in as 1:In the mixed solution of 1 EC and DEC；
Using celgard as membrane, pure lithium is used as to electrode；Glove box (the H being assembled in full of argon gas atmosphere of related battery2O,
O2：<1 ppm) in carry out；The constant current charge-discharge test of battery carries out charge and discharge on Neware BTS3000 battery test systems
Electrical testing, test environment maintain 25 DEG C of constant temperature, and the voltage range of test is 2.5 ~ 4.5 V, as a result as shown in Fig. 1 to 5.
As shown in the figure, Fig. 1 is the uncoated tertiary cathode material and manganese Base Metal organic frame prepared in embodiment
The XRD diagram of the tertiary cathode material of compound cladding, it can be seen that the diffraction maximum of two kinds of materials is all very sharp, diffraction maximum and stratiform α-
NaFeO2Structure, diffraction maximum is consistent, illustrates that material crystalline prepared by coprecipitation method is fine, is deposited without obvious impurities phase
；Substantially division occurs for diffraction maximum (006)/(102) and (108)/(110), illustrates that material all has good layer structure,
Also indicate that cladding does not cause the structure of material to change at the same time.
Fig. 2 is the uncoated tertiary cathode material and manganese Base Metal organic frame compound cladding prepared in embodiment
The SEM figures of tertiary cathode material, there it can be seen that material prepared by coprecipitation method is showed by the bar-shaped little particle aggregation of piece
The two level near-spherical structure formed, manganese Base Metal organic frame compound do not change the pattern of material after coating.
Fig. 3 be embodiment in prepare manganese Base Metal organic frame compound cladding tertiary cathode material TEM figure and
HR-TEM schemes, from the graph, it is apparent that the surface of spherical ternary cathode material has successfully coated manganese Base Metal organic frame
Compound.
Fig. 4 is the uncoated tertiary cathode material and manganese Base Metal organic frame compound cladding prepared in embodiment
Cycle performance figure of the tertiary cathode material under 0.5 C current densities, the mA g of 1 C=200-1, the material circulation after cladding stablizes
Property and capacity retention ratio have a significant raising, after constant current charge-discharge 50 encloses, 175.2 mAh of specific discharge capacity of material after cladding
g-1Apparently higher than uncoated 123.4 mAh g of tertiary cathode material-1。
Fig. 5 is the uncoated tertiary cathode material and manganese Base Metal organic frame compound cladding prepared in embodiment
High rate performance figure of the tertiary cathode material under different current densities, the mA g of 1 C=200-1, the charge and discharge under 0.5 C current densities
Electrical testing circulates, and specific discharge capacity is 178.1 mAh g-1；The charge-discharge test circulation under 1 C current densities, specific discharge capacity
For 165.5 mAh g-1；The charge-discharge test circulation under 2 C current densities, specific discharge capacity are 149.7 mAh g-1；In 5 C
Charge-discharge test circulation under current density, specific discharge capacity are 132.3 mAh g-1；The charge-discharge test under 10 C current densities
Circulation, specific discharge capacity is 122.5 mAh g-1；When current density is again lowered to 1 C and 0.5 C low current densities from 10 C
During lower charge-discharge test circulation, specific discharge capacity gos up to 148.1 mAh g-1And 145.3 mAh g-1, but less than small electricity first
Specific discharge capacity under current density charge and discharge cycles state.And the tertiary cathode material of manganese Base Metal organic frame compound cladding
Cyclical stability and high rate capability have significant raising, the charge-discharge test circulation under 0.5 C current densities, and discharge ratio
Capacity is 196.7 mAh g-1；The charge-discharge test circulation under 1 C current densities, specific discharge capacity are 191.2 mAh g-1；
Charge-discharge test circulation under 2 C current densities, specific discharge capacity are 183.6 mAh g-1；The charge and discharge electrical measurement under 5 C current densities
Examination circulation, specific discharge capacity is 172.0 mAh g-1；The charge-discharge test circulation under 10 C current densities, specific discharge capacity are
156.4 mAh g-1；When current density is again lowered to charge-discharge test circulation under 1 C and 0.5 C low current densities from 10 C
When, specific discharge capacity can effectively go up to 186.2 mAh g-1And 191.4 mAh g-1, filled relative to low current density first
Specific discharge capacity under discharge cycles state is not almost decayed.
Claims (10)
- A kind of 1. ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding, it is characterised in that：The material Material realizes the cladding to spherical ternary cathode material using the self assembly performance of MOFs materials by simple one-step method.
- 2. the ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding according to claim 1, It is characterized in that：The material has layer structure, exists without impurities phase, and cladding does not cause the structure of material to change.
- 3. the ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding according to claim 1, It is characterized in that：The material has the two level near-spherical structure formed by the bar-shaped little particle aggregation of piece.
- 4. the ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding according to claim 1 Preparation method, it is characterised in that comprise the following steps：Step 1）The preparation of presoma, configures certain density nickel, cobalt, manganese Metal mixed salt solution, while configures a certain concentration Carbonate solution as precipitating reagent, under protective atmosphere, above two solution is distinguished by peristaltic pump with certain speed Constantly it is pumped into reactor, at the same time, suitable ammonia spirit is added dropwise and adjusts pH；In reaction process, precise control of temperature, PH and mixing speed, ageing a period of time after reaction, by the product after above-mentioned ageing, by filtering, washing, in certain bar Under part presoma is obtained after drying；Step 2）The preparation of spherical ternary cathode material, by step 1）The presoma, with certain chemical dosage ratio, claims with lithium source Take presoma and Li2CO3After ground and mixed is uniform, calcine under certain condition, spherical tertiary cathode material is made after natural cooling Material；Step 3）The preparation of the tertiary cathode material of manganese Base Metal organic frame compound cladding, with metal manganese salt, organic carboxyl acid Meet the ratio between amount of certain material with spherical anode material, metal manganese salt and organic carboxyl acid are dissolved in solvent, and add step Rapid 2）Gained spherical ternary cathode material, stirring after a certain period of time, enclose reaction kettle, carry out hydro-thermal reaction, and above-mentioned hydro-thermal is anti- Answer product, by filtering, washing, dry under certain condition after, be made the lithium of manganese Base Metal organic frame compound cladding from Sub- battery tertiary cathode material.
- 5. preparation method according to claim 4, it is characterised in that：The step 1）In lithium source be Li2CO3Or LiOH·H2O, metal salt are sulfate or acetate, and precipitating reagent is sodium carbonate or ammonium hydrogen carbonate, in reaction process, temperature control At 45 ~ 80 DEG C, 7.5 ~ 9, mixing speed is controlled in 800 ~ 1200 rpm/min, after reaction digestion time control for pH controls For system in 10 ~ 18 h, washing process uses deionized water, and vacuum drying condition is that 12 ~ 24 h are kept at 50 ~ 80 DEG C.
- 6. preparation method according to claim 4, it is characterised in that：The step 2）In presoma and lithium source chemistry Dose ratio is 1：1.05 ~ 1.10, calcining heat is 800 ~ 900 DEG C.
- 7. preparation method according to claim 4, it is characterised in that：The step 3）Metal manganese salt, organic carboxyl acid and ball The ratio between amount of material of shape positive electrode is 2:1:（100~400）.
- 8. preparation method according to claim 4, it is characterised in that：The step 3）Middle manganese salt is manganese acetate or chlorination Manganese, organic carboxyl acid are 2,5-Dihydroxyterephthalic acid, solvent DMF, ethanol and deionized water.
- 9. preparation method according to claim 4, it is characterised in that：The step 3）Hydrothermal reaction condition be 70-120 DEG C, the reaction time is 2-6 h, the step 3）Filtering and washing process in repeatedly washed using organic solvent, it is described Step 3）Drying condition be 50 ~ 80 DEG C be dried in vacuo 12 ~ 24 h after, in 160 ~ 250 DEG C of 6 ~ 12 h of forced air drying.
- 10. the ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding according to claim 1 Application as cell positive material, it is characterised in that：After 0.5 C constant current charge-discharges 50 circle, specific discharge capacity is 160 ~ 180 mAh g-1, under 10 C high magnifications, specific discharge capacity is 140 ~ 160 mAh g-1。
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