CN107658432A - The preparation method and its positive electrode of modified metal-oxide positive electrode - Google Patents
The preparation method and its positive electrode of modified metal-oxide positive electrode Download PDFInfo
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- CN107658432A CN107658432A CN201610593827.7A CN201610593827A CN107658432A CN 107658432 A CN107658432 A CN 107658432A CN 201610593827 A CN201610593827 A CN 201610593827A CN 107658432 A CN107658432 A CN 107658432A
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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
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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
- H01M4/48—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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- 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
- H01M4/52—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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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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 invention provides a kind of preparation method of the modified metal-oxide positive electrode for lithium ion battery, preparation process including lithium manganese phosphate presoma and/or iron manganese phosphate for lithium presoma, the step of above-mentioned presoma mixes with metal oxide precursor, and the step of high-temperature process realizes cladding is carried out to mixed product.Present invention also offers a kind of modified metal-oxide positive electrode, including covering material and encapsulated material, the covering material is lithium manganese phosphate and/or iron manganese phosphate for lithium, and the encapsulated material is a kind of positive electrode.The modified metal-oxide positive electrode of the present invention, overcomes the defects of existing lithium ion anode material can not have high-energy-density, long-life and high safety performance concurrently, has good cyclical stability, specific capacity height.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery modified anode material, and its modification prepared using this method
Positive electrode.
Background technology
With energy crisis and environmental problem getting worse, the development and application of electric car turns into the focus of whole world research.Generation
Overwhelming majority of countries provides policy and financial support Development of EV industry in boundary, and China is using ev industry as automobile
Transition and upgrade and the emerging strategic industries first developed, carry forward vigorously the exploitation and application of new-energy automobile.In new energy vapour
During car fast development, many problems are also faced with, wherein, restricting one of principal element of electric car development is
Power battery performance.In the whole composition of dynamic lithium battery, positive electrode has a very important status, positive electrode into
Originally the 1/3 of lithium ion battery is constituted about.In this context, the positive pole of high-energy-density, long-life, high safety performance is developed
Development of the material to dynamic lithium battery is most important.
The positive electrode that usual dynamic lithium battery uses, mainly there is cobalt acid lithium, LiMn2O4, LiFePO4 and ternary material etc..
Cobalt acid lithium is a kind of positive electrode of comparative maturity, but expensive, and service life is short, is unfavorable for environmental protection.LiMn2O4 into
This is low, and security is higher, and deficiency is that theoretical capacity is not high.LiFePO4 heat endurance is good, safe, and shortcoming is than energy
Metric density is low.Ternary metal oxide positive electrode LiNi1-x-yCoxMnyO2Combine cobalt acid lithium, lithium nickelate and LiMn2O4 three
The advantages of kind positive electrode, there is the advantages of energy density is high, advantage of lower cost, have in dynamic lithium battery application non-
Often big potentiality.The deficiency of ternary material is that safety and stability is poor, is come especially for the nickel cobalt manganese anode material of rich nickel
Say, when material exposes in atmosphere, side reaction easily occurs with the moisture in air, cause surface alkali content rise, sternly
Processing and the performance of material are have impact on again.
Patent application CN104733730A uses lithium manganese phosphate composite L iMn(1-x)MxPO4/ C (M Ti, Co, Fe,
Mg etc.) method for handling ternary material is coated, the discharge and recharge blanking voltage of lithium ion battery is improved, first with hydro-thermal method
Lithium manganese phosphate composite is prepared, is then mixed with nickel-cobalt-manganese ternary material, the patent procedure method is simple, but utilizes water
Hot method prepares lithium manganese phosphate composite and is difficult to realize large-scale production, and reaction needs to carry out at high temperature.Patent application
Iron manganese phosphate lithium material is coated on the surface of nickel cobalt aluminum, this side using the method for dry method cladding by CN104577093A
The advantages of method is the stability for improving positive electrode, does not produce waste liquid during cladding simultaneously without high temperature sintering, exists
Deficiency be simple being uniformly distributed by physical mixed two kinds of materials difficult to realize.
The content of the invention
The invention provides a kind of preparation method of the modified metal-oxide positive electrode for lithium ion battery, and use
Modified metal-oxide positive electrode prepared by method as described above.
The preparation method of modified metal-oxide positive electrode of the present invention, including lithium manganese phosphate presoma and/or manganese phosphate
The preparation process of iron lithium presoma, the step of above-mentioned presoma mixes with metal oxide precursor, and to mixed product
Carry out the step of high-temperature process realizes cladding.
Present invention also offers a kind of modified metal-oxide positive electrode prepared according to above-mentioned preparation method, the modified gold
Category oxide anode material includes covering material and encapsulated material, and the covering material is lithium manganese phosphate and/or iron manganese phosphate
Lithium, its chemical formula are LiMn(1-x)FexPO4, 0≤x ＜ 1；The encapsulated material is metal oxide, the metal oxide
Can be separately as the positive electrode of lithium ion battery.In the present invention, encapsulated material can be selected from nickle cobalt lithium manganate (NCM),
Nickel cobalt lithium aluminate (NCA) and at least one of positive electrode with concentration gradient.Wherein, covering material lithium manganese phosphate
And/or it is 0.5%~15% that iron manganese phosphate for lithium, which accounts for the mass fraction of modified metal-oxide positive electrode, preferred covering material phosphoric acid
The mass fraction that manganese lithium and/or iron manganese phosphate for lithium account for modified metal-oxide positive electrode is 1.0%~5.0%.Lithium manganese phosphate and phosphorus
The poorly conductive of sour ferromanganese lithium, if cladding can excessively cause the decay of metal oxide materials electric conductivity, coated at least
Uniform cladding can not be realized, it is impossible to produce a desired effect.The average grain of the covering material lithium manganese phosphate and/or iron manganese phosphate for lithium
Footpath is 50~300nm.
According to another object of the present invention, there is provided a kind of lithium rechargeable battery, including positive pole, negative pole, electrolyte and every
Film, the positive pole include modified metal-oxide positive electrode as described above.
According to the purpose of the present invention, there is provided a kind of preparation side of modified metal-oxide positive electrode for lithium ion battery
Method, comprise the following steps：
(a) lithium source, source of iron, manganese source and phosphorus source, and/or lithium source, manganese source and phosphorus source are configured to mixed solution；
(b) a kind of complexing agent is provided；
(c) mixed solution in step (a) and complexing agent are reacted in a solvent, then by filtering, washing and
Dry, lithium manganese phosphate presoma and/or iron manganese phosphate for lithium presoma is made；
(d) lithium manganese phosphate presoma and/or iron manganese phosphate for lithium presoma are mixed with organic carbon source, then with before metal oxide
Body mixing is driven, then carries out ball milling；
(e) modified metal-oxide positive electrode is made in the product after ball milling in step (d) after high-temperature process.
In the present invention, lithium source is selected from least one of lithium dihydrogen phosphate, lithium acetate, lithium nitrate and lithium sulfate；Source of iron is selected from
At least one of ferrous sulfate, ferrous acetate and ferrous nitrate；Manganese source is in manganese sulfate, manganese nitrate and manganese citrate
It is at least one；Phosphorus source is selected from least one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid.In step (a), lithium source,
The mol ratio (1.0~1.1) of source of iron, manganese source and phosphorus source：(0~0.9)：(0.1~1)：1, rubbed according to the element of lithium, iron, manganese and phosphorus
You are than meter.The solvent of mixed solution is water in step (a).
According to one embodiment of the present invention, mixed solution further adds antioxidant in step (a), described anti-oxidant
Agent is selected from least one of vitamin C, carotenoid and iso-ascorbic acid.Antioxidant and the mass ratio of manganese source and source of iron
For 1:10~1:100.Antioxidant is added, can prevent bivalent manganese and ferrous iron from aoxidizing during the course of the reaction.
In the present invention, preferably complexing agent is enveloping agent solution, and the addition of complexing agent can control pattern and the reaction of presoma
PH value.The complexing agent is selected from least one of ammoniacal liquor, citric acid and triethanolamine.
In step (c), the mixed solution in step (a) and complexing agent can be added drop-wise in solvent under stirring
Row reaction, the pH value for controlling reaction system are 3.0~8.0.The solvent be selected from polyethylene glycol, diglycol and go from
At least one of sub- water, the rotating speed of stirring is 400~1000rpm, and time for adding is 3~5h；The reaction temperature of the reaction
Spend for 40~110 DEG C, the reaction time is 5~12h.Subsequently dry temperature is 80 DEG C, and 8~16 are dried in vacuum drying chamber
H, lithium manganese phosphate presoma and/or iron manganese phosphate for lithium presoma is made.
In step (d), organic carbon source is selected from least one of sucrose, glucose, vitamin C and citric acid；Wherein,
Lithium manganese phosphate presoma and/or iron manganese phosphate for lithium presoma, the mass ratio with organic carbon source are 5:1~20:1.Before metal oxide
The granular size for driving body is 0.5~20 μm, directly can buy or make by oneself.The time of ball milling is 0.5h~5h, ball milling
Rotating speed is 200~500rpm.
According to one embodiment of the present invention, metal oxide precursor includes nickel cobalt manganese presoma, nickel cobalt aluminium presoma etc.,
It can generally prepare with the following method：By the nickel salts, cobalt salt, manganese salt (or aluminium salt) of solubility according to certain
Mol ratio be dissolved in appropriate deionized water, metallic element Ni, Co, Mn (or Al) mol ratio could be arranged to 3:3:3、
5:3:2、6:2:2 and 8:1:1 etc., it is used as precipitating reagent, ammonia spirit conduct by the use of alkaline solution (such as sodium hydroxide solution)
Complexing agent, charging rate is controlled, reaction temperature is 40~70 DEG C, speed of agitator 600-1000rpm, controls reaction system
PH value is 9~12, reacts 10~24h, filtered, washing, vacuum drying.
According to another embodiment of the invention, metal oxide precursor can also be the positive electrode with concentration gradient
Presoma, formula are (NixMnyCoz)(OH)2, wherein 0.5<x<1,0<y<0.3,0<z<0.3,0<x+y+z<1, can be with
Prepare with the following method：Nickel salt, cobalt salt and the manganese salt hybrid metal solution of high nickel content are configured first in the first raw material tank
In, nickel salt, cobalt salt and the manganese salt hybrid metal solution of then preparing high Mn content are placed in the second raw material tank.In course of reaction,
Solution in second raw material tank is continuously inputted in the first raw material tank, in mixed first raw material tank and the second raw material tank
Metallic solution, precipitating reagent, complexing agent are added by way of cocurrent adding material in intensively stirred reactor, keep 400-800rpm
Mixing speed, reaction temperature be 40~70 DEG C, pH value be 9~12, react 8~30h, it is filtered, washing, vacuum drying
.
In step (e), the high-temperature process includes multi-segment program temperature control high-temperature process, and the multistage comprises at least more than two sections.
Preferably, the product after ball milling in step (d) is put into tube furnace, is warming up to 300~500 DEG C, sinter 2~4h, then
700~900 DEG C are warming up to, 5~20h is sintered, then naturally cools to room temperature；It is highly preferred that by ball milling in step (d)
Product afterwards is put into tube furnace, is warming up to 300~500 DEG C, sinters 2~4h, then is warming up to 750-850 DEG C, sinters 8-12
H, then naturally cool to room temperature.Above-mentioned whole high-temperature process is carried out in inert gas, and inert gas can be selected from nitrogen
At least one of gas, argon gas and helium.Above-mentioned temperature-rise period is preferably heated up with 1~5 DEG C/min programming rate.
Using modified metal-oxide positive electrode made from the preparation method of the present invention, existing lithium ion anode material is overcome
The defects of material can not have high-energy-density, long-life and high safety performance concurrently, there is good cyclical stability, specific capacity height.
Above-mentioned preparation method is simple to operate, is easy to large-scale production, reduces the pH value of metal oxide cathode material surface, has
Production, storage beneficial to material, increase the service life.
Brief description of the drawings
Fig. 1：The SEM figures of the positive electrode prepared for the embodiment of the present invention 1；
Fig. 2：The XRD spectra of the positive electrode prepared for the embodiment of the present invention 1 and comparative example 1；
Fig. 3：The first charge-discharge curve map of the positive electrode prepared for the embodiment of the present invention 1 and comparative example 1；
Fig. 4：The specific discharge capacity cycle performance figure of the positive electrode prepared for the embodiment of the present invention 1 and comparative example 1；
Fig. 5：The specific discharge capacity cycle performance figure of the positive electrode prepared for the embodiment of the present invention 2 and comparative example 2.
Embodiment
The present invention is described in detail following specific embodiment, but the present invention is not restricted to following examples.
Embodiment 1：
Weigh 20.28g MnSO4.H2O, 8.34g FeSO4.7H2O, 0.29g vitamin C, 17.30g purity be 85% it is dense
Phosphoric acid, 80mL deionized waters and the in the mixed solvent of 70mL polyethylene glycol are dissolved in, obtains solution A；Weigh 12.60g
LiOH.H2O is dissolved in 300mL deionized waters, obtains B solution；Weigh the concentrated ammonia liquor that 12.58g concentration is 25%~28%
Solution, it is diluted in 500mL volumetric flasks, is configured to enveloping agent solution.
Reaction temperature is controlled at 50 DEG C, and the rotating speed of stirring is 600rpm, adds 250mL deionized waters and the poly- second of 250mL
Glycol controls the rate of addition of A, B solution and enveloping agent solution, the pH value of reaction, which controls, is respectively as reaction bottom liquid
6.0, the time that solution is added dropwise is 3h, reaction time 8h.Then filtered, washed, placed into 80 DEG C of vacuum and do
Dry case 12h, iron manganese phosphate for lithium precursor compound is obtained by grinding sieving.
Precursor compound obtained above is mixed with sucrose, the mass ratio of sucrose and presoma is 1：5.7, then again with
Nickel cobalt manganese precursor compound (being purchased from Jin Chi energy and materials Co., Ltd, its granular size is 8 μm) and lithium carbonate mixing,
Nickel cobalt manganese precursor compound and lithium carbonate mol ratio are 1:0.53, using planetary ball mill, rotating speed is arranged to 300rpm, ball
Consume time as 1h.
Sample after ball milling is sintered, is put into tube furnace and is heated up with 5 DEG C/min programming rates, when being warming up to 300 DEG C,
2h is sintered, is continuously heating at 850 DEG C, 10h is sintered, naturally cools to room temperature, whole sintering process uses N2As
Gas is protected, modified metal-oxide positive electrode is obtained by ground 200 eye mesh screen.
Comparative example 1：
The nickel cobalt manganese precursor compound of quality in the same manner as in Example 1 is weighed, and is according to presoma and lithium carbonate mol ratio
1:0.53 adds lithium source mixing, is directly sintered, is put into tube furnace with 5 DEG C/min programming rates without any processing
Heating, when being warming up to 300 DEG C, 2h is sintered, is continuously heating at 850 DEG C, sintered 10h, naturally cool to room temperature, it is whole
Individual sintering process uses N2As protection gas, nickel cobalt manganese anode material (unmodified metal is obtained by ground 200 eye mesh screen
Oxide anode material).
Detain electrically prepared：
Positive electrode using the positive electrode that embodiment 1 and comparative example 1 obtain as lithium ion battery respectively, with lithium metal
Piece is that negative material is prepared into CR2025 button cells, and the process specifically prepared is：By positive electrode, conductive black, gather
Vinylidene is 90 according to weight ratio:5:5 are dissolved in 1-METHYLPYRROLIDONE, are coated on after stirring on aluminium foil,
It is dried in vacuo at 100 DEG C, obtains positive plate.Barrier film uses polypropylene diaphragm, and electrolyte uses 1.0mol/L LiPF6/ (carbon
Vinyl acetate+dimethyl carbonate+methyl ethyl carbonate), it is assembled into button cell in the glove box full of Ar gas.
Electrochemical property test：
Tested for charge-discharge property, at room temperature, constant-current charge is extremely cut to 4.3V, then constant-voltage charge under 0.1C multiplying powers
Only electric current is 0.01C, then under 0.1C multiplying powers constant-current discharge to 2.5V, theoretical specific capacity 160mAh/g；For following
The test in ring life-span, using constant-current charge under 1.0C multiplying powers to 4.3V, then constant-voltage charge to cut-off current is 0.01C, then
Constant-current discharge is to 2.5V under 1.0C multiplying powers.
Embodiment 2：
Weigh 20.28g MnSO4.H2O, 8.34g FeSO4.7H2O, 0.29g vitamin C, 17.30g purity are 85%
Concentrated phosphoric acid, 80mL deionized waters and the in the mixed solvent of 70mL diglycols are dissolved in, obtains solution A；Weigh
12.60g LiOH.H2O is dissolved in 300mL deionized waters, obtains B solution；It is 25%~28% to weigh 12.58g concentration
Concentrated ammonia solution, be diluted in 500mL volumetric flasks, be configured to enveloping agent solution.
Reaction temperature is controlled at 60 DEG C, and the rotating speed of stirring is 600rpm, adds 250mL deionized waters and 250mL mono- contracts
Rate of addition of the diethylene glycol as reaction bottom liquid, respectively control A, B solution and enveloping agent solution, the pH value control of reaction
8.0 are made as, the time that solution is added dropwise is 3h, reaction time 10h.Then filtered, washed, place into 80 DEG C very
Empty drying box 12h, iron manganese phosphate for lithium precursor compound is obtained by grinding sieving.
Precursor compound obtained above is mixed with sucrose, the mass ratio of sucrose and presoma is 1：9, then with nickel cobalt aluminium
Precursor compound (being purchased from Jin Chi energy and materials Co., Ltd, its granular size is 8 μm) and lithium carbonate mixing, nickel cobalt aluminium
Precursor compound and lithium carbonate mol ratio are 1:0.53, using planetary ball mill, rotating speed is arranged to 300rpm, Ball-milling Time
For 2h.
Sample after ball milling is sintered, is put into tube furnace and is heated up with 5 DEG C/min programming rates, when being warming up to 500 DEG C,
2h is sintered, is continuously heating to 820 DEG C, 8h is sintered, naturally cools to room temperature, whole sintering process uses N2As protection
Gas, modified metal-oxide positive electrode is obtained by ground 200 eye mesh screen.
Comparative example 2：
Weigh the nickel cobalt aluminium precursor compound of quality in the same manner as in Example 2 and be 1 according to presoma and lithium carbonate mol ratio:
0.53 adds lithium source mixing, is directly sintered, is put into tube furnace with 5 DEG C/min programming rate liters without any processing
Temperature, when being warming up to 500 DEG C, 2h is sintered, is continuously heating to 820 DEG C, 8h is sintered, naturally cools to room temperature, it is whole to burn
Knot process uses N2As protection gas, obtaining nickel cobalt aluminium positive electrode by ground 200 eye mesh screen, (unmodified metal aoxidizes
Thing positive electrode).
Detain electrically prepared：
The positive electrode of the positive electrode as the lithium ion battery that are obtained respectively using embodiment 2 and comparative example 2 prepares button electricity
Pond, specific method are same as above.
Electrochemical property test：
Tested for charge-discharge property, at room temperature, constant-current charge is extremely cut to 4.3V, then constant-voltage charge under 0.1C multiplying powers
Only electric current is 0.01C, then under 0.1C multiplying powers constant-current discharge to 2.5V, theoretical specific capacity 180mAh/g；For following
The test in ring life-span, using constant-current charge under 1.0C multiplying powers to 4.3V, then constant-voltage charge to cut-off current is 0.01C, then
Constant-current discharge is to 2.5V under 1.0C multiplying powers.
Embodiment 3：
Weigh 25.35g MnSO4.H2O, 0.51g carotenoid, 17.30g purity are 85% concentrated phosphoric acid, are dissolved in 50mL
The in the mixed solvent of deionized water and 100mL polyglycols, obtains solution A；Weigh 6.30g LiOH.H2O is dissolved in 150mL
In deionized water, B solution is obtained；The concentrated ammonia solution that 12.58g concentration is 25%~28% is weighed, is diluted to 500mL
In volumetric flask, enveloping agent solution is configured to.
Reaction temperature is controlled at 60 DEG C, and the rotating speed of stirring is 800rpm, adds 250mL deionized waters and 250mL poly- two
Rate of addition of the alcohol as reaction bottom liquid, respectively control A, B solution and enveloping agent solution, the pH value control of reaction is 6.0,
The time that solution is added dropwise is 3h, reaction time 10h.Then filtered, washed, place into 80 DEG C of vacuum drying chambers
12h, lithium manganese phosphate precursor compound is obtained by grinding sieving.
Precursor compound obtained above is mixed with sucrose, the mass ratio of sucrose and presoma is 1：9, then with nickel cobalt manganese
Precursor compound (being purchased from Jin Chi energy and materials Co., Ltd, its granular size is 3 μm) and lithium carbonate mixing, nickel cobalt manganese
Precursor compound and lithium carbonate mol ratio are 1:0.53, using planetary ball mill, rotating speed is arranged to 300rpm, Ball-milling Time
For 2h.
Sample after ball milling is sintered, is put into tube furnace and is heated up with 5 DEG C/min programming rates, when being warming up to 500 DEG C
Under, 3h is sintered, is continuously heating at 850 DEG C, 10h is sintered, naturally cools to room temperature, whole sintering process uses N2
As protection gas, modified metal-oxide positive electrode is obtained by ground 200 eye mesh screen.
Electrochemical property test method similar embodiment 1.
Embodiment 4：
Weigh 12.68g MnSO4.H2O, 20.85g FeSO4.7H2O, 1.65g vitamin C, 17.30g purity are 85%
Concentrated phosphoric acid, be dissolved in 80mL deionized waters and the in the mixed solvent of 70mL polyethylene glycol, obtain solution A；Weigh 12.60
g LiOH.H2O is dissolved in 300mL deionized waters, obtains B solution；Weigh the dense ammonia that 12.58g concentration is 25%~28%
The aqueous solution, it is diluted in 500mL volumetric flasks, is configured to enveloping agent solution.
Reaction temperature is controlled at 80 DEG C, and the rotating speed of stirring is 500rpm, adds 200mL deionized waters and 300mL mono- contracts
Rate of addition of the diethylene glycol as reaction bottom liquid, respectively control A, B solution and enveloping agent solution, the pH value control of reaction
8.0 are made as, the time that solution is added dropwise is 5h, reaction time 5h.Then filtered, washed, place into 80 DEG C very
Empty drying box 12h, iron manganese phosphate for lithium precursor compound is obtained by grinding sieving.
Precursor compound obtained above is mixed with sucrose, the mass ratio of sucrose and presoma is 1：9, then with nickel cobalt aluminium
Persursor material (being purchased from Jin Chi energy and materials Co., Ltd, its granular size is 5 μm) and lithium carbonate mix, before nickel cobalt aluminium
It is 1 to drive body material and lithium carbonate mol ratio:0.53, using planetary ball mill, rotating speed is arranged to 200rpm, Ball-milling Time 2h.
Sample after ball milling is sintered, is put into tube furnace and is heated up with 5 DEG C/min programming rates, when being warming up to 300 DEG C
Under, 3h is sintered, is continuously heating at 800 DEG C, 12h is sintered, naturally cools to room temperature, whole sintering process uses N2
As protection gas, modified metal-oxide positive electrode is obtained by ground 200 eye mesh screen.
Electrochemical property test method similar embodiment 2
Table 1, the embodiment of the present invention 1 and 2 and the positive electrode surface pH value prepared by comparative example 1 and 2 contrast
| Test sample | Test temperature | Mean ph value |
| Uncoated nickel cobalt manganese (comparative example 1) | 25.2 | 11.9 |
| Coat nickel cobalt manganese (embodiment 1) | 25.1 | 11.0 |
| Uncoated nickel cobalt aluminium (comparative example 2) | 25.1 | 11.8 |
| Coat nickel cobalt aluminium (embodiment 2) | 25.2 | 10.8 |
PH method of testings：Tested using plum Teller S220 pH meters, pH meter demarcated first, demarcation complete with
Carry out the test of sample again afterwards.Then sample 5g is accurately weighed, is put into 250mL glass beakers, then adds 45g
Deionized water, magnetic agitation filtering, take sample clarified solution to pour into clean vial, sealed to constant room after 10 minutes
Temperature is to be measured.Each sample surveys 3 Duplicate Samples, and records pH value and temperature, by the way that mean ph value is calculated.
Table 1 is that the embodiment of the present invention 1 and 2 contrasts with the positive electrode surface pH value prepared by comparative example 1 and 2, is not carried out
The metal oxide cathode material surface pH value of cladding is higher, by coating a certain amount of lithium manganese phosphate or iron manganese phosphate for lithium,
The pH value of material surface is reduced to 11.0 or so.
Fig. 1 is the SEM figures of the modified metal-oxide positive electrode prepared by the embodiment of the present invention 1, as seen from the figure, in nickel
The Surface coating of cobalt manganese anode material has a small amount of iron manganese phosphate lithium material, and particle diameter is 300nm or so.Fig. 2 is implemented for the present invention
Modification and the XRD spectra of unmodified metal oxide cathode material, positive electrode prepared by example 1 and comparative example 1 is being wrapped
Cover the XRD spectra before and after iron manganese phosphate lithium material and significant change does not occur, find no obvious iron manganese phosphate for lithium and mutually deposit
.Fig. 3 be modification prepared by the embodiment of the present invention 1 and comparative example 1 and unmodified metal oxide cathode material first
Charging and discharging curve figure, test condition：Voltage range is 2.5~4.3V, discharge and recharge under 0.1C multiplying powers, iron manganese phosphate for lithium cladding nickel
The sample of cobalt manganese all forms a land regions in charge and discharge process, and the phenomenon that overcharges for preventing nickel cobalt manganese material is beneficial to.
Fig. 4 is modification prepared by the embodiment of the present invention 1 and comparative example 1 and unmodified metal oxide cathode material in 1C charge and discharges
Under electric multiplying power, 2.5V~4.3V specific discharge capacity cycle performance figure；Fig. 5 is prepared by the embodiment of the present invention 2 and comparative example 2
Modification and unmodified metal oxide cathode material under 1C charge-discharge magnifications, the circulation of 2.5V~4.3V specific discharge capacity
Performance map, the nickel cobalt aluminum specific discharge capacity after cladding is handled somewhat is reduced, but cyclical stability is substantially carried
It is high.
Claims (23)
1. a kind of preparation method of modified metal-oxide positive electrode, comprises the following steps：
(a) lithium source, source of iron, manganese source and phosphorus source, and/or lithium source, manganese source and phosphorus source are configured to mixed solution；
(b) a kind of complexing agent is provided；
(c) mixed solution in step (a) and complexing agent are reacted in a solvent, then by filtering, washing and
Dry, lithium manganese phosphate presoma and/or iron manganese phosphate for lithium presoma is made；
(d) lithium manganese phosphate presoma and/or iron manganese phosphate for lithium presoma are mixed with organic carbon source, then with before metal oxide
Body mixing is driven, then carries out ball milling；
(e) modified metal-oxide positive electrode is made in the product after ball milling in step (d) after high-temperature process.
2. preparation method according to claim 1, it is characterised in that the lithium source be selected from lithium dihydrogen phosphate, lithium acetate,
At least one of lithium nitrate and lithium sulfate.
3. preparation method according to claim 1, it is characterised in that the source of iron be selected from ferrous sulfate, ferrous acetate and
At least one of ferrous nitrate.
4. preparation method according to claim 1, it is characterised in that the manganese source is selected from manganese sulfate, manganese nitrate and lemon
At least one of sour manganese.
5. preparation method according to claim 1, it is characterised in that phosphorus source is selected from diammonium hydrogen phosphate, biphosphate
At least one of ammonium and phosphoric acid.
6. preparation method according to claim 1, it is characterised in that in step (a), according to lithium, iron, manganese and phosphorus
Elemental mole ratios meter, lithium source, source of iron, the mol ratio (1.0~1.1) of manganese source and phosphorus source：(0~0.9)：(0.1~1)：1.
7. preparation method according to claim 1, it is characterised in that mixed solution further adds anti-in step (a)
Oxidant, the antioxidant are selected from least one of vitamin C, carotenoid and iso-ascorbic acid.
8. preparation method according to claim 1, it is characterised in that the complexing agent is selected from ammoniacal liquor, citric acid and three second
At least one of hydramine.
9. preparation method according to claim 1, it is characterised in that in step (c) reaction, control reactant
The pH value of system is between 3.0~8.0.
10. preparation method according to claim 1, it is characterised in that in step (c), the solvent is selected from poly- second two
At least one of alcohol, diglycol and deionized water.
11. preparation method according to claim 1, it is characterised in that in step (c), the reaction temperature of the reaction
For 40~110 DEG C, the reaction time is 5~12h.
12. preparation method according to claim 1, it is characterised in that in step (d), organic carbon source be selected from sucrose,
At least one of glucose, vitamin C and citric acid；Lithium manganese phosphate presoma and/or iron manganese phosphate for lithium presoma,
Mass ratio with organic carbon source is 5:1~20:1.
13. preparation method according to claim 1, it is characterised in that in step (d), the metallic oxide precursor
Body is nickel cobalt manganese presoma, nickel cobalt aluminium presoma or the positive electrode material precursor with concentration gradient.
14. preparation method according to claim 1, it is characterised in that in step (d), the time of the ball milling is 0.5
H~5h.
15. preparation method according to claim 1, it is characterised in that in step (e), the high-temperature process includes two
Section procedure above temperature control high temperature processing step.
16. preparation method according to claim 15, it is characterised in that the high-temperature process includes：By step (d)
Product after middle ball milling is warming up to 300~500 DEG C, sinters 2~4h, then is warming up to 700~850 DEG C, sinters 5~15h.
17. preparation method according to claim 16, it is characterised in that the high-temperature process is carried out in inert gas,
Inert gas is selected from least one of nitrogen, argon gas and helium.
18. a kind of modified metal-oxide positive electrode, is made using preparation method as claimed in claim 1.
19. modified metal-oxide positive electrode according to claim 18, including covering material and encapsulated material, institute
It is lithium manganese phosphate and/or iron manganese phosphate for lithium to state covering material, and the encapsulated material is selected from nickle cobalt lithium manganate (NCM),
Nickel cobalt lithium aluminate (NCA) and at least one of positive electrode with concentration gradient.
20. modified metal-oxide positive electrode according to claim 19, it is characterised in that the covering material, which accounts for, to be changed
Property metal oxide cathode material mass fraction be 0.5%~15%.
21. modified metal-oxide positive electrode according to claim 20, it is characterised in that the covering material, which accounts for, to be changed
Property metal oxide cathode material mass fraction be 1.0%~5.0%.
22. modified metal-oxide positive electrode according to claim 19, it is characterised in that the covering material is put down
Equal particle diameter is 50~300nm.
23. a kind of lithium rechargeable battery, including positive pole, negative pole, electrolyte and barrier film, the positive pole includes such as claim
Modified metal-oxide positive electrode described in 18.
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| CN109244602A (en) * | 2018-08-27 | 2019-01-18 | 中国科学院大学 | A kind of method of modifying of lithium-air battery electrolyte |
| CN110061231A (en) * | 2019-05-17 | 2019-07-26 | 中伟新材料有限公司 | A kind of nickelic tertiary cathode material of modification and preparation method thereof |
| CN110649235A (en) * | 2019-09-12 | 2020-01-03 | 江苏容汇通用锂业股份有限公司 | Modification method of nickel-rich ternary cathode material |
| CN113942990A (en) * | 2021-08-25 | 2022-01-18 | 北京当升材料科技股份有限公司 | Lithium manganese iron phosphate precursor, lithium manganese iron phosphate positive electrode material, preparation method of lithium manganese iron phosphate positive electrode material, electrode and lithium ion battery |
| CN114256448A (en) * | 2020-09-25 | 2022-03-29 | 比亚迪股份有限公司 | Lithium iron manganese phosphate composite material, preparation method thereof and lithium ion battery |
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