CN109786734A - A kind of preparation method of the nickelic positive electrode of lithium secondary battery - Google Patents
A kind of preparation method of the nickelic positive electrode of lithium secondary battery Download PDFInfo
- Publication number
- CN109786734A CN109786734A CN201811155576.XA CN201811155576A CN109786734A CN 109786734 A CN109786734 A CN 109786734A CN 201811155576 A CN201811155576 A CN 201811155576A CN 109786734 A CN109786734 A CN 109786734A
- Authority
- CN
- China
- Prior art keywords
- lithium
- preparation
- positive electrode
- secondary battery
- sintering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation methods of the nickelic positive electrode of lithium secondary battery, optimization is improved to preparation process, the nickelic ternary material of available effective element doping, under the premise of keeping material stratiform structurally consummate, the specific capacity cycle life for effectively improving material avoids being reduced for excessive Li/Ni mixing and nickel ion, and sintering atmosphere is unrestricted, it can be any one of air, oxygen or nitrogen or combine, production technology is more flexible.The invention also discloses a kind of nickelic positive electrodes of lithium secondary battery.
Description
Technical field
The invention belongs to battery technology fields, and in particular to a kind of preparation method of the nickelic positive electrode of lithium secondary battery.
Background technique
Relative to other secondary cell systems, for lithium ion battery due to its energy density height, self discharge is small, has extended cycle life
Etc. advantages be widely used in notebook, in the digital electronic goods such as mobile phone.Although early in 1873, British Robert
Davidson is manufactured that first electro-tricycle using zinc iron cell on the basis of carriage for the first time, but due to early stage battery
Excessively heavy, energy density and cycle life cannot be met the requirements.With tesla's Model S pure electric vehicle passenger car in 2012
Formal offline delivery consumer, especially environment in recent years pollution get worse and the fluctuation of oil price, lithium-ion electric
The development of the pure electric automobile of pond driving increasingly cause government and enterprise in terms of concern.
A key factor of limitation pure electric automobile development is exactly that its course continuation mileage can't sufficiently meet people at present
Life requirement.Therefore, high-energy density is developed, the anode material for lithium-ion batteries of long circulation life becomes more more and more urgent.
Wherein the materials such as the positive electrode of nickelic system especially NCA and NCM811 are due to its higher discharge capacity and voltage platform,
Cause extensive concern and the research of people.
Although the high-nickel materials such as nickel cobalt lithium aluminate have relatively high charging and discharging capacity, in material system, nickel contains
The structural stability of the raising of amount, material is deteriorated.It is especially embodied in the preparation process of nickelic three element material, in order to complete
The generation of layer structure avoids excessive Li/Ni mixing and nickel from being reduced into divalent, optimal with the raising of nickel content
Sintering temperature needs constantly to reduce.
But in order to promote structural stability of the nickelic ternary material in battery charging and discharging cyclic process, transition metal element
Doping is necessary key means again.But introducing transition metal element usually requires higher in the mixing sintering step of volume production
Sintering temperature just can guarantee that doped chemical is introduced into the ontology of material, really play effective chanza.This itself and height
Nickel ternary material needs lower sintering temperature to contradict, and is especially embodied in doping type high-nickel material preparation process.
It is a kind of into lithium secondary battery ternary nickel cobalt manganese anode material introduce doped chemical method be in ternary precursor
Preparation process in introduce and want the element that is doped, usually by the element of desired doping during co-precipitation
Soluble-salt is introduced into ternary nickel cobalt mn sulphate system, while passing through ammonium hydroxide and complexing, that is, pH value of sodium hydroxide solution etc.
The regulation of parameter is to achieve the purpose that co-precipitation.Such as application No. is 03153034.6 patents, will be thought using the method for co-precipitation
The soluble-salt of the element and ontology element to be adulterated, the doping type hydroxide being co-precipitated by sodium hydroxide.But by
It is limited to the influence that wet process co-precipitation prepares presoma sedimentation equilibrium constant, it is desirable to which different metal element co-precipitation is still limited by
The influence of element species and content.As the patent of application number 200410101824.4 passes through sol-gal process for doped chemical, sheet
Element of volume and organic acid complexing agent prepare the presoma of doping type, but this method is related to organic matter calcining, and there are environmental pollution wind
Danger, industrial application face larger difficulty.And it is usually all ontology introducing by introducing doped chemical in presoma, and nickelic material
Material structural damage be usually all by the surface texture with electrolyte contacts, the doping of effective surface layer cannot be formed, it is real
The effect is unsatisfactory on border.For another example application No. is 201710883429.3 patents, utilize class monocrystalline precursor preparation monocrystalline pattern
Nickelic positive electrode.But be limited to preparation class monocrystalline precursor liquid body additives, wetting agent use, actual fabrication process compared with
For complexity, and it is related to the combustion decomposition reaction of organic matter, and prefabrication process temperature is lower, it is difficult to which realization was effectively adulterated
Journey, therefore actual application has difficulties.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of nickelic positive electrodes of lithium secondary battery
Preparation method, by optimizing preparation process, the nickelic ternary material of available effective element doping is keeping material stratiform
Under the premise of structurally consummate, effectively improve the specific capacity cycle life of material, avoid excessive Li/Ni mixing and nickel from
Son is reduced.
It is a further object of the present invention to provide a kind of nickelic positive electrodes of lithium secondary battery.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of preparation method of the nickelic positive electrode of lithium secondary battery, includes the following steps:
1) by Ni1-yCoy(OH)2Or Ni1-y-zCoyMnz(OH)2Or Ni1-y-zCoyAlz(OH)2, doped chemical M compound
It is ground up, sieved to obtain the Li of the M containing doped chemical after soak is sintered and cooled to room temperature after mixing with lithium sourcexNi1-yCoyO2
Or LixNi1-y-zCoyMnzO2Or LixNi1-y-zCoyAlzO2Oxide among product, 0 < x≤0.6,0 < y < 0.4.
2) by product among the oxide of the M containing doped chemical obtained in step 1) and lithium source according to molar ratio 1: (1-x) is mixed
It closes to carry out being ground up, sieved after soak is sintered and cooled to room temperature after mixing and obtains the lithium secondary battery comprising doped chemical M
Nickelic positive electrode.
Further, in step 1), the lithium source is selected from lithium hydroxide, lithium carbonate, and one in lithium phosphate or lithium nitrate
Kind is a variety of.
Further, the temperature range that soak sintering is carried out in step 1) is 800-1100 DEG C, preferably 850-1000
℃。
Further, the liter in step 1) before progress soak sintering according to 1-5 DEG C/min (preferably 1-2 DEG C/min)
Warm rate is warming up to 350~450 DEG C.
Further, the middle atmosphere for carrying out soak sintering of step 1) can be one in oxygen, air or nitrogen
Kind is a variety of.
Further, the doped chemical M is one of Al, Mn, Ti, Zr, Sn, W, Mo, Mg, V or a variety of.
Further, the compound of doped chemical M described in step 1) is the oxide, hydroxide, sulphur of doped chemical M
Hydrochlorate, chlorate, nitrate it is one or more.
Further, in step 2), the lithium source is selected from lithium hydroxide, lithium carbonate, and one in lithium phosphate or lithium nitrate
Kind is a variety of.
Further, the atmosphere for soak sintering being carried out in step 2) can be one of oxygen, air or a variety of.
Further, the temperature range that soak sintering is carried out in step 2) is 650-950 DEG C, preferably 750-850 DEG C.
A kind of nickelic positive electrode of lithium secondary battery prepared using the above method, general formula LiNi1-y-zCoyMzO2, M choosing
From one of Al, Mn, Ti, Zr, Sn, W, Mo, Mg, V or a variety of, 0 < y <, 0.4,0 < z <, 0.4,0 < y+z < 0.4.
Further, the median particle diameter of the nickelic positive electrode of the lithium secondary battery is 2-20 μm.
In addition, can also be realized by any means known nickelic to above-mentioned lithium secondary battery under central idea of the invention
The cladding of positive electrode.Covering material can be aluminium oxide, titanium oxide, zirconium oxide, magnesia, zinc oxide and its otide containing lighium
One or more combinations of object, li-contained phosphate.Doped chemical can be one kind of the elements such as magnesium, aluminium, titanium, zirconium, manganese, nickel, niobium
Or multiple combinations.
The advantages of lithium secondary battery of the present invention nickelic positive electrode, is as follows:
(1) present invention passes through the Li to generate doping M elementxNi1-yCoyO2Oxide among product be means, Ke Yi
Realize that doped chemical is efficiently entering the lattice of material at higher temperature, at the same time since the preparation of intermediate product can not be related to
The generation of positive electrode stratiform structure effectively prevents high temperature for the aggravation and destruction of Li/Ni mixing.As adopted in embodiment 1
With the mode of step sintering, the doping of element can be realized at a high temperature of 950 DEG C, gained sample capacity can achieve
203mAh/g.And comparative example 1 uses traditional sintering processing, high temperature causes serious Li/Ni mixing, the discharge capacity of sample
It is lower with first charge discharge efficiency.
(2) present invention is in the Li for generating doping M elementxNi1-yCoyO2Oxide among during product, pass through introducing
A certain amount of lithium compound can penetrate into material by the hole of presoma under the action of melting agent as melting agent, doped chemical
Material is internal, relative to simple granular solids/solid particle contact, can effectively facilitate doped chemical M and be efficiently entering material sheet
Body is unlikely to still to be adsorbed on bulk material surface in the form of nano particle, to realize doped chemical depth and content
Regulation, and sintering atmosphere is unrestricted, can be any one of air, oxygen or nitrogen or combines, production technology is more
Flexibly.
(3) present invention can be sintered the intermediate product of pre-doping in suitable temperature by the Optimal improvements of preparation process
Under the conditions of be prepared into the nickelic ternary material of doping type, can be realized at a lower temperature in double sintering lattice relaxation and
It grows perfect, overcomes the contradiction of doped chemical, Li/Ni mixing, chemical property etc. under the conditions of high temperature sintering, obtain electricity
The excellent doping type high-nickel material of chemical property.
Detailed description of the invention
Fig. 1 and Fig. 2 is the SEM image of positive electrode sample in embodiment 1 and comparative example 1.
Fig. 3 is all discharge curves of head of positive electrode sample in embodiment 1 and comparative example 1.
Fig. 4 is in embodiment 1 and 100 weeks cycle performance curves of 1 positive electrode sample of comparative example.
Specific embodiment
With reference to embodiments, the present invention is further explained.But these embodiments be only limitted to illustrate the present invention rather than
Limit the scope of application of the invention.
Embodiment 1
One) Li is prepared0.2Ni0.8Co0.1Mn0.1O2Oxide
By lithium carbonate, nano-manganese dioxide and Ni0.8Co0.1(OH)2It is mixed according to molar ratio 0.1: 0.1: 1.It will mix
Raw material after conjunction in air atmosphere according to 2 DEG C/min of heating rate by room temperature to 350 DEG C, keep the temperature 5 DEG C/min liter after 3h
Temperature to 950 DEG C of calcining 5h, cooled to room temperature obtains the Li of doping type0.2Ni0.8Co0.1Mn0.1O2Product among oxide,
About 10 μm of median particle diameter.
Two) LiNi is prepared0.8Co0.1Mn0.1O2Positive electrode
The oxide centre product that lithium hydroxide and step 1 obtain are mixed according to molar ratio 0.8: 1.After mixing
Powder after 750 DEG C of calcining 10h, obtain LiNi in oxygen0.8Co0.1Mn0.1O2Lithium-containing oxides, about 11 μm of median particle diameter,
As shown in Figure 1.
Using N-Methyl pyrrolidone as solvent, by gained powder after sintering and conductive black and Kynoar according to weight
It is coated on the surface of clean aluminium foil, blade coating film forming after mixing evenly than 90: 5: 5.Electrode slice is punched into diameter after forced air drying
The disk of 8mm, further 120 DEG C of drying 6h remove moisture in vacuum drying oven.Using the electrode slice made as half-cell
Working electrode, lithium metal are to electrode, with 1mol/L LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and
The weight ratio 1 of DMC: 1) being used as electrolyte, and battery is assembled into glove box and carries out charge-discharge test, voltage model to its battery
It encloses for 2.8-4.25V, charging and discharging currents density is 0.1C, and discharge curve and cycle performance are as shown in Figures 3 and 4.
Embodiment 2
One) Li is prepared0.3Ni0.8Co0.1Mn0.095Zr0.005O2Oxide
By lithium nitrate, nano zirconium dioxide and Ni0.8Co0.1Mn0.095(OH)2It is mixed according to molar ratio 0.3: 0.005: 1
It closes.By mixed raw material in air atmosphere according to 1 DEG C/min of heating rate by room temperature to 350 DEG C, keep the temperature 3h after 5
DEG C/min is warming up to 1000 DEG C of calcining 5h, cooled to room temperature obtains the Li of doping type0.3Ni0.8Co0.1Mn0.095Zr0.005O2
Product among oxide, about 8.5 μm of median particle diameter.
Two) LiNi is prepared0.8Co0.1Mn0.095Zr0.005O2Positive electrode
The oxide centre product that lithium hydroxide and step 1 obtain are mixed according to molar ratio 0.7: 1.After mixing
Powder after 850 DEG C of calcining 10h, obtain LiNi in oxygen0.8Co0.1Mn0.095Zr0.005O2Lithium-containing oxides, median particle diameter
About 9.5 μm.
Using N-Methyl pyrrolidone as solvent, by gained powder after sintering and conductive black and Kynoar according to weight
It is coated on the surface of clean aluminium foil, blade coating film forming after mixing evenly than 90: 5: 5.Electrode slice is punched into diameter after forced air drying
The disk of 8mm, further 120 DEG C of drying 6h remove moisture in vacuum drying oven.Using the electrode slice made as half-cell
Working electrode, lithium metal are to electrode, with 1mol/L LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and
The weight ratio 1 of DMC: 1) being used as electrolyte, and battery is assembled into glove box and carries out charge-discharge test, voltage model to its battery
It encloses for 2.8-4.25V, charging and discharging currents density is 0.1C.
Embodiment 3
One) Li is prepared0.01Ni0.8Co0.1Mn0.095Zr0.005O2Oxide
By lithium hydroxide, nano zirconium dioxide and Ni0.8Co0.1Mn0.095(OH)2It is carried out according to molar ratio 0.01: 0.005: 1
Mixing.By mixed raw material in air atmosphere according to 3 DEG C/min of heating rate by room temperature to 350 DEG C, keep the temperature 3h after 5
DEG C/min is warming up to 1000 DEG C of calcining 5h, cooled to room temperature obtains the Li of doping type0.01Ni0.8Co0.1Mn0.095Zr0.005O2
Product among oxide, about 9 μm of median particle diameter.
Two) LiNi is prepared0.8Co0.1Mn0.095Zr0.005O2Positive electrode
The oxide centre product that lithium hydroxide and step 1 obtain are mixed according to molar ratio 0.99: 1.After mixing
Powder after 820 DEG C of calcining 10h, obtain LiNi in oxygen0.8Co0.1Mn0.095Zr0.005O2Lithium-containing oxides, median particle diameter
About 10 μm.
Using N-Methyl pyrrolidone as solvent, by gained powder after sintering and conductive black and Kynoar according to weight
It is coated on the surface of clean aluminium foil, blade coating film forming after mixing evenly than 90: 5: 5.Electrode slice is punched into diameter after forced air drying
The disk of 8mm, further 120 DEG C of drying 6h remove moisture in vacuum drying oven.Using the electrode slice made as half-cell
Working electrode, lithium metal are to electrode, with 1mol/L LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and
The weight ratio 1 of DMC: 1) being used as electrolyte, and battery is assembled into glove box and carries out charge-discharge test, voltage model to its battery
It encloses for 2.8-4.25V, charging and discharging currents density is 0.1C.
Embodiment 4
One) Li is prepared0.01Ni0.8Co0.1Mn0.095W0.005O2Oxide
By lithium hydroxide, nano tungsten trioxide and Ni0.8Co0.1Mn0.095(OH)2It is carried out according to molar ratio 0.01: 0.005: 1
Mixing.By mixed raw material in air atmosphere according to 2 DEG C/min of heating rate by room temperature to 350 DEG C, keep the temperature 3h after 5
DEG C/min is warming up to 950 DEG C of calcining 5h, cooled to room temperature obtains the Li of doping type0.01Ni0.8Co0.1Mn0.095W0.005O2Oxygen
Product among compound, about 18 μm of median particle diameter.
Two) LiNi is prepared0.8Co0.1Mn0.095W0.005O2Positive electrode
The oxide centre product that lithium hydroxide and step 1 obtain are mixed according to molar ratio 0.99: 1.After mixing
Powder after 950 DEG C of calcining 5h, obtain LiNi in oxygen0.8Co0.1Mn0.095W0.005O2Lithium-containing oxides, median particle diameter is about
20μm。
Using N-Methyl pyrrolidone as solvent, by gained powder after sintering and conductive black and Kynoar according to weight
It is coated on the surface of clean aluminium foil, blade coating film forming after mixing evenly than 90: 5: 5.Electrode slice is punched into diameter after forced air drying
The disk of 8mm, further 120 DEG C of drying 6h remove moisture in vacuum drying oven.Using the electrode slice made as half-cell
Working electrode, lithium metal are to electrode, with 1mol/L LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and
The weight ratio 1 of DMC: 1) being used as electrolyte, and battery is assembled into glove box and carries out charge-discharge test, voltage model to its battery
It encloses for 2.8-4.25V, charging and discharging currents density is 0.1C.
Embodiment 5
One) Li is prepared0.01Ni0.8Co0.1Mn0.095Zr0.005O2Oxide
By lithium hydroxide, nano zirconium dioxide and Ni0.8Co0.1Mn0.095(OH)2It is carried out according to molar ratio 0.01: 0.005: 1
Mixing.By mixed raw material in nitrogen atmosphere according to 2 DEG C/min of heating rate by room temperature to 350 DEG C, keep the temperature 3h after 5
DEG C/min is warming up to 850 DEG C of calcining 5h, cooled to room temperature obtains the Li of doping type0.01Ni0.8Co0.1Mn0.095Zr0.005O2
Product among oxide, about 15 μm of median particle diameter.
Two) LiNi is prepared0.8Co0.1Mn0.095Zr0.005O2Positive electrode
The oxide centre product that lithium hydroxide and step 1 obtain are mixed according to molar ratio 0.99: 1.After mixing
Powder after 800 DEG C of calcining 10h, obtain LiNi in oxygen0.8Co0.1Mn0.095Zr0.005O2Lithium-containing oxides, median particle diameter
About 16 μm.
Using N-Methyl pyrrolidone as solvent, by gained powder after sintering and conductive black and Kynoar according to weight
It is coated on the surface of clean aluminium foil, blade coating film forming after mixing evenly than 90: 5: 5.Electrode slice is punched into diameter after forced air drying
The disk of 8mm, further 120 DEG C of drying 6h remove moisture in vacuum drying oven.Using the electrode slice made as half-cell
Working electrode, lithium metal are to electrode, with 1mol/L LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and
The weight ratio 1 of DMC: 1) being used as electrolyte, and battery is assembled into glove box and carries out charge-discharge test, voltage model to its battery
It encloses for 2.8-4.25V, charging and discharging currents density is 0.1C.
Embodiment 6
One) Li is prepared0.6Ni0.8Co0.1Mn0.095Zr0.005O2Oxide
By lithium hydroxide, nano zirconium dioxide and Ni0.8Co0.1Mn0.095(OH)2It is carried out according to molar ratio 0.6: 0.005: 1
Mixing.By mixed raw material in air atmosphere according to 2 DEG C/min of heating rate by room temperature to 350 DEG C, keep the temperature 3h after 5
DEG C/min is warming up to 950 DEG C of calcining 5h, cooled to room temperature obtains the Li of doping type0.01Ni0.8Co0.1Mn0.095Zr0.005O2
Product among oxide, about 2 μm of median particle diameter.
Two) LiNi is prepared0.8Co0.1Mn0.095Zr0.005O2Positive electrode
The oxide centre product that lithium hydroxide and step 1 obtain are mixed according to molar ratio 0.4: 1.After mixing
Powder after 850 DEG C of calcining 10h, obtain LiNi in oxygen0.8Co0.1Mn0.095Zr0.005O2Lithium-containing oxides, median particle diameter
About 3um.
Using N-Methyl pyrrolidone as solvent, by gained powder after sintering and conductive black and Kynoar according to weight
It is coated on the surface of clean aluminium foil, blade coating film forming after mixing evenly than 90: 5: 5.Electrode slice is punched into diameter after forced air drying
The disk of 8mm, further 120 DEG C of drying 6h remove moisture in vacuum drying oven.Using the electrode slice made as half-cell
Working electrode, lithium metal are to electrode, with 1mol/L LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and
The weight ratio 1 of DMC: 1) being used as electrolyte, and battery is assembled into glove box and carries out charge-discharge test, voltage model to its battery
It encloses for 2.8-4.25V, charging and discharging currents density is 0.1C.
Embodiment 7
Three) Li is prepared0.6Ni0.8Co0.1Al0.095Zr0.005O2Oxide
By lithium hydroxide, nano zirconium dioxide and Ni0.8Co0.1Al0.095(OH)2It is carried out according to molar ratio 0.6: 0.005: 1
Mixing.By mixed raw material in air atmosphere according to 2 DEG C/min of heating rate by room temperature to 350 DEG C, keep the temperature 3h after 5
DEG C/min is warming up to 950 DEG C of calcining 5h, cooled to room temperature obtains the Li of doping type0.01Ni0.8Co0.1Mn0.095Zr0.005O2
Product among oxide, about 2 μm of median particle diameter.
Four) LiNi is prepared0.8Co0.1Al0.095Zr0.005O2Positive electrode
The oxide centre product that lithium hydroxide and step 1 obtain are mixed according to molar ratio 0.4: 1.After mixing
Powder after 650 DEG C of calcining 10h, obtain LiNi in oxygen0.8Co0.1Al0.095Zr0.005O2Lithium-containing oxides, median particle diameter
About 3 μm.
Using N-Methyl pyrrolidone as solvent, by gained powder after sintering and conductive black and Kynoar according to weight
It is coated on the surface of clean aluminium foil, blade coating film forming after mixing evenly than 90: 5: 5.Electrode slice is punched into diameter after forced air drying
The disk of 8mm, further 120 DEG C of drying 6h remove moisture in vacuum drying oven.Using the electrode slice made as half-cell
Working electrode, lithium metal are to electrode, with 1mol/L LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and
The weight ratio 1 of DMC: 1) being used as electrolyte, and battery is assembled into glove box and carries out charge-discharge test, voltage model to its battery
It encloses for 2.8-4.25V, charging and discharging currents density is 0.1C.
Comparative example 1
By lithium hydroxide, nano zirconium dioxide and Ni0.8Co0.1Mn0.095(OH)2It is mixed according to molar ratio 1: 0.005: 1
It closes.By mixed raw material, 5 DEG C/min is warming up to 950 DEG C of calcining 5h in oxygen atmosphere, and cooled to room temperature is adulterated
The LiNi of type0.8Co0.1Mn0.095Zr0.005O2Positive electrode, about 10.5 μm of median particle diameter, as shown in Figure 2.
Using N-Methyl pyrrolidone as solvent, by gained powder after sintering and conductive black and Kynoar according to weight
It is coated on the surface of clean aluminium foil, blade coating film forming after mixing evenly than 90: 5: 5.Electrode slice is punched into diameter after forced air drying
The disk of 8mm, further 120 DEG C of drying 6h remove moisture in vacuum drying oven.Using the electrode slice made as half-cell
Working electrode, lithium metal are to electrode, with 1mol/L LiPF6/ vinyl carbonate (EC)-dimethyl carbonate (DMC) (EC and
The weight ratio 1 of DMC: 1) being used as electrolyte, and battery is assembled into glove box and carries out charge-discharge test, voltage model to its battery
It encloses for 2.8-4.25V, charging and discharging currents density is 0.1C, and discharge curve and cycle performance are as shown in Figures 3 and 4.
The electrochemistry circulation of above-described embodiment the results are shown in Table 1:
Table 1 (charging and discharging capacity=charge/discharge capacity/combination electrode material quality)
As seen from the above table, the available Effective Doping of material after improving according to the technical solution in the present invention is nickelic
Material body, thus with relatively good capacity performance and cyclical stability.
Claims (10)
1. a kind of preparation method of the nickelic positive electrode of lithium secondary battery, includes the following steps:
1) by Ni1-yCoy(OH)2Or Ni1-y-zCoyMnz(OH)2Or Ni1-y-zCoyAlz(OH)2, doped chemical M compound and lithium
Source is ground up, sieved to obtain the Li of the M containing doped chemical after soak is sintered and cooled to room temperature after mixingxNi1-yCoyO2Or
LixNi1-y-zCoyMnzO2Or LixNi1-y-zCoyAlzO2Oxide among product, 0 < x≤0.6,0 < y < 0.4；
2) by product among the oxide of the M containing doped chemical obtained in step 1) and lithium source according to molar ratio 1: (1-x) mixes mixed
Carry out being ground up, sieved that obtain the lithium secondary battery comprising doped chemical M nickelic after even after soak is sintered and cooled to room temperature
Positive electrode.
2. preparation method as described in claim 1, which is characterized in that in step 1), the lithium source is selected from lithium hydroxide, carbonic acid
Lithium, one of lithium phosphate or lithium nitrate or a variety of.
3. preparation method as described in claim 1, which is characterized in that carry out the temperature range of soak sintering in step 1)
It is 800-1100 DEG C.
4. preparation method as described in claim 1, which is characterized in that according to 1- before progress soak sintering in step 1)
The heating rate of 5 DEG C/min is warming up to 350~450 DEG C.
5. preparation method as described in claim 1, which is characterized in that the atmosphere for carrying out soak sintering in step 1) is oxygen
One of gas, air or nitrogen are a variety of.
6. preparation method as described in claim 1, which is characterized in that the doped chemical M be A1, Mn, Ti, Zr, Sn, W,
One of Mo, Mg, V or a variety of, the compound of doped chemical M described in step 1) are the oxide of doped chemical M, hydroxide
Object, sulfate, chlorate, nitrate it is one or more.
7. preparation method as described in claim 1, which is characterized in that in step 2), the lithium source is selected from lithium hydroxide, carbonic acid
Lithium, one of lithium phosphate or lithium nitrate or a variety of.
8. preparation method as described in claim 1, which is characterized in that the atmosphere for carrying out soak sintering in step 2) is oxygen
One of gas, air are a variety of, and the temperature range for carrying out soak sintering is 650-950 DEG C.
9. a kind of nickelic positive electrode of lithium secondary battery using any the method preparation of the claims 1 to 8, general formula are
LiNi1-y-zCoyMzO2, M is selected from one of Al, Mn, Ti, Zr, Sn, W, Mo, Mg, V or a variety of, 0 < y <, 0.4,0 < z <
0.4,0 < y+z < 0.4.
10. a kind of nickelic positive electrode of lithium secondary battery as claimed in claim 9, which is characterized in that the lithium secondary battery
The median particle diameter of nickelic positive electrode is 2-20 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811155576.XA CN109786734A (en) | 2018-09-29 | 2018-09-29 | A kind of preparation method of the nickelic positive electrode of lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811155576.XA CN109786734A (en) | 2018-09-29 | 2018-09-29 | A kind of preparation method of the nickelic positive electrode of lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109786734A true CN109786734A (en) | 2019-05-21 |
Family
ID=66496285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811155576.XA Pending CN109786734A (en) | 2018-09-29 | 2018-09-29 | A kind of preparation method of the nickelic positive electrode of lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109786734A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330059A (en) * | 2019-06-25 | 2019-10-15 | 浙江工业大学 | A kind of sintering process of the nickelic positive electrode of high stability lithium ion |
| CN112054239A (en) * | 2020-09-14 | 2020-12-08 | 昆山宝创新能源科技有限公司 | Electrolyte and application thereof |
| CN113851633A (en) * | 2021-11-29 | 2021-12-28 | 中南大学 | Niobium-doped high-nickel ternary cathode material coated with niobium phosphate and preparation method thereof |
| CN114512645A (en) * | 2021-12-29 | 2022-05-17 | 有研科技集团有限公司 | High-nickel positive electrode material, preparation method thereof and lithium secondary battery |
| CN114843488A (en) * | 2022-06-14 | 2022-08-02 | 远景动力技术(江苏)有限公司 | Positive electrode active material, electrochemical device, and electronic device |
| EP4253328A1 (en) * | 2020-11-30 | 2023-10-04 | Panasonic Intellectual Property Management Co., Ltd. | Nonaqueous electrolyte secondary battery positive electrode and nonaqueous electrolyte secondary battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104241633A (en) * | 2014-09-11 | 2014-12-24 | 北大先行科技产业有限公司 | Gradient-doping positive material of lithium ion battery and preparation method of gradient-doping positive material of lithium ion battery |
| CN106910882A (en) * | 2017-04-01 | 2017-06-30 | 济南大学 | A kind of lithium ion battery preparation method of large single crystal layered cathode material |
| CN107311242A (en) * | 2017-08-10 | 2017-11-03 | 济南大学 | A kind of lithium ion battery improved preparation method of large single crystal layered cathode material |
| CN108545785A (en) * | 2018-03-07 | 2018-09-18 | 格林美（无锡）能源材料有限公司 | A kind of large single crystal nickel cobalt manganese anode material and preparation method thereof |
-
2018
- 2018-09-29 CN CN201811155576.XA patent/CN109786734A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104241633A (en) * | 2014-09-11 | 2014-12-24 | 北大先行科技产业有限公司 | Gradient-doping positive material of lithium ion battery and preparation method of gradient-doping positive material of lithium ion battery |
| CN106910882A (en) * | 2017-04-01 | 2017-06-30 | 济南大学 | A kind of lithium ion battery preparation method of large single crystal layered cathode material |
| CN107311242A (en) * | 2017-08-10 | 2017-11-03 | 济南大学 | A kind of lithium ion battery improved preparation method of large single crystal layered cathode material |
| CN108545785A (en) * | 2018-03-07 | 2018-09-18 | 格林美（无锡）能源材料有限公司 | A kind of large single crystal nickel cobalt manganese anode material and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330059A (en) * | 2019-06-25 | 2019-10-15 | 浙江工业大学 | A kind of sintering process of the nickelic positive electrode of high stability lithium ion |
| CN110330059B (en) * | 2019-06-25 | 2022-04-01 | 浙江工业大学 | Sintering process of high-stability lithium ion high-nickel cathode material |
| CN112054239A (en) * | 2020-09-14 | 2020-12-08 | 昆山宝创新能源科技有限公司 | Electrolyte and application thereof |
| EP4253328A1 (en) * | 2020-11-30 | 2023-10-04 | Panasonic Intellectual Property Management Co., Ltd. | Nonaqueous electrolyte secondary battery positive electrode and nonaqueous electrolyte secondary battery |
| CN113851633A (en) * | 2021-11-29 | 2021-12-28 | 中南大学 | Niobium-doped high-nickel ternary cathode material coated with niobium phosphate and preparation method thereof |
| CN113851633B (en) * | 2021-11-29 | 2022-04-08 | 中南大学 | Niobium-doped high-nickel ternary cathode material coated with niobium phosphate and preparation method thereof |
| CN114512645A (en) * | 2021-12-29 | 2022-05-17 | 有研科技集团有限公司 | High-nickel positive electrode material, preparation method thereof and lithium secondary battery |
| CN114843488A (en) * | 2022-06-14 | 2022-08-02 | 远景动力技术(江苏)有限公司 | Positive electrode active material, electrochemical device, and electronic device |
| CN114843488B (en) * | 2022-06-14 | 2024-03-26 | 远景动力技术(江苏)有限公司 | Positive electrode active material, electrochemical device, and electronic device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109786734A (en) | A kind of preparation method of the nickelic positive electrode of lithium secondary battery | |
| CN106129360B (en) | A kind of high-tap density lithium-rich manganese-based anode material and preparation method thereof | |
| CN110050366A (en) | For lithium secondary battery nickel hydroxide active material presoma, be used to prepare nickel hydroxide active material presoma method, by method prepare for the nickel hydroxide active material of lithium secondary battery and with the positive lithium secondary battery comprising nickel hydroxide active material | |
| KR20190035670A (en) | Spherical or Spherical-like Cathode Material for a Lithium Battery, a battery and preparation method and application thereof | |
| KR101007504B1 (en) | Cathode material for lithium secondary battery and method for manufacturing of as the same | |
| CN110817972B (en) | Fluorine modified high-voltage lithium cobaltate, preparation method thereof and battery | |
| JP2011096650A (en) | Cathode active material particle powder, method of manufacturing the same, and nonaqueous electrolyte secondary battery | |
| CN108140831B (en) | Positive electrode active material for lithium secondary battery and positive electrode comprising same | |
| KR20030032363A (en) | A method of preparing a positive active material for a lithium secondary battery | |
| CN110226251A (en) | Nickel hydroxide active material presoma and preparation method thereof, nickel hydroxide active material and lithium secondary battery | |
| CN106602004A (en) | High-safety power lithium ion secondary battery composite positive material and preparation method thereof | |
| CN103094550A (en) | Preparation method of lithium-rich anode material | |
| EP4322257A1 (en) | Cobalt-free positive electrode material, preparation method therefor, and application thereof | |
| CN110518221B (en) | Method for preparing lithium silicate coated lithium nickel cobalt manganese oxide positive electrode material by anti-solvent method | |
| CN109155431B (en) | Lithium ion secondary battery | |
| CN110459764B (en) | Lithium ion battery positive electrode material and preparation method and application thereof | |
| KR100805910B1 (en) | Olivine type positive active material for lithium battery, method for preparing the same, and lithium battery comprising the same | |
| JPWO2020027158A1 (en) | Positive electrode active material for lithium ion secondary batteries, manufacturing method of positive electrode active material for lithium ion secondary batteries, lithium ion secondary batteries | |
| CN106946296B (en) | A kind of micron order monocrystalline lithium nickelate and its preparation method and application | |
| CN100472853C (en) | Lithium-contained composite metal oxide material of lamina structure and use thereof | |
| KR101405663B1 (en) | Positive active material for rechargeable, method for preparing the same, and rechargeable lithium battery comprising the same | |
| Tian et al. | Application prospects of high-voltage cathode materials in all-solid-state lithium-ion batteries | |
| CN115050940B (en) | High-entropy ceramic modified cathode material and preparation method and application thereof | |
| CN115881913A (en) | High-nickel positive electrode material, preparation method, positive plate, battery and electric device | |
| CN116190593A (en) | Lithium battery positive electrode material with mixed phase structure, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190521 |