CN105470495B - The positive electrode and preparation method thereof and lithium ion battery of a kind of positive active material and preparation method thereof, lithium ion battery - Google Patents
The positive electrode and preparation method thereof and lithium ion battery of a kind of positive active material and preparation method thereof, lithium ion battery Download PDFInfo
- Publication number
- CN105470495B CN105470495B CN201410452137.0A CN201410452137A CN105470495B CN 105470495 B CN105470495 B CN 105470495B CN 201410452137 A CN201410452137 A CN 201410452137A CN 105470495 B CN105470495 B CN 105470495B
- Authority
- CN
- China
- Prior art keywords
- lithium
- active material
- positive active
- manganese
- positive electrode
- 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.)
- Active
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of positive active material and preparation method thereof, the positive electrode and preparation method thereof of lithium ion battery and lithium ion batteries containing the positive electrode, the positive active material contains nickel cobalt manganese oxidate for lithium and the iron manganese phosphate lithium compound shown in formula (1), for the particles coat of the iron manganese phosphate lithium compound in the surface of the particle of the nickel cobalt manganese oxidate for lithium and gap between the particle of the nickel cobalt manganese oxidate for lithium, the average grain diameter of the particle of the iron manganese phosphate lithium compound is 30 200nm；LiMnxFe1‑xPO4 (1), wherein 0 ＜ x ＜ 1, preferably 0.5≤x≤0.8, more preferably 0.6≤x≤0.8.According to positive electrode provided by the invention, there is higher compacted density and higher energy density, the lithium ion battery containing the positive electrode, with higher capacity and with superior charge-discharge performance and security performance.
Description
Technical field
The present invention relates to a kind of positive active material and preparation method thereof, contain the lithium ion battery of the positive active material
Positive electrode and preparation method thereof and the lithium ion battery containing the positive electrode.
Background technology
Lithium ion battery is most widely used battery in the products such as current mobile phone, laptop, automobile.And lithium ion
Important composition of the positive electrode of battery as lithium ion battery affects the capacity, discharge performance and safety of lithium ion battery
Performance etc. receives the extensive concern of researcher.
CN101212048A discloses a kind of positive electrode of lithium rechargeable battery and the battery containing the positive electrode,
The positive electrode is by the phosphate metal lithium salts active material of olivine structural and transition metal oxidate for lithium or coated
Then transition metal oxidate for lithium active material is assembled into lithium battery, to change by being mixed to get with conductive agent, glue caking agent
The security performance of kind lithium rechargeable battery and capacity, heavy-current discharge performance, cycle performance and the high temperature for improving secondary cell
Storge quality.But phosphate metal lithium salts and transition metal oxidate for lithium are existed in the form of secondary aggregate, are all μm
The bulk shape of rank, two kinds of material are difficult to evenly dispersed, also, phosphate metal lithium salts and transition metal oxidate for lithium are in anode
It is to exist with individual two kinds of active materials in pole piece, is divided into two-phase, it is difficult to play the complementation of two kinds of materials.
CN102249208A discloses a kind of hydrothermal synthesis method of ion battery positive pole material manganese lithium phosphate iron lithium, the party
Method is to be stirred lithium hydroxide, phosphoric acid, ferrous sulfate and manganese sulfate, is then transferred into closed reactor, certain
Filtration washing is carried out after reacting a few hours under pressure (0.48-1MPa) and certain temperature (150-180 DEG C), is then added soluble
Carbon source (such as glucose, sucrose, starch, phenolic resin) is stirred dispersion, then carries out spray drying the latter's expansion drying,
Finally by the powder after drying, (600-750 DEG C) is sintered packet carbon acquisition iron manganese phosphate lithium material at high temperature.But the party
Method needs the expensive lithium source using more times, causes manufacturing cost higher；Lithium sulfate remains after reaction, it is necessary to increase process and be washed
It washs and the precipitation in later stage extraction lithium sulfate, the process and cost for increasing preparation process is unfavorable for industrialized production；In addition it is making
When standby precursor solution, a variety of insoluble molysite, a variety of insoluble manganese salts and a variety of insoluble lithium salts are will produce, ingredient is more, in hydro-thermal
It is difficult to ensure that various composition is uniform, consistent dispersion and reacts to each other in reaction process, also, due to LiFePO4 and manganese phosphate
The Ksp of lithium is different, and it is not synchronous homogeneous precipitation that can cause two kinds of ingredients, can all cause the uneven of final product.
Therefore, there is an urgent need for exploitation one kind having high-energy density, high magnification, high compacted density and good safety for this field
The positive electrode of lithium ion battery and preparation method thereof of energy.
Invention content
The purpose of the present invention cannot have both high-energy density and height to overcome in existing anode material for lithium-ion batteries
Security performance and the complex and high cost defect of the preparation method of existing positive electrode, provide a kind of positive active material and
Preparation method and have containing the positive electrode active materials high-energy density and high safety performance lithium ion battery positive material
Material and preparation method thereof and the lithium ion battery containing the positive electrode.
The present inventor by the study found that the iron manganese phosphate for lithium of definite composition with the particle form packet of 30-200nm
It overlays on obtained in the particle surface of nickel cobalt manganese oxidate for lithium and the gap between the particle of the nickel cobalt manganese oxidate for lithium
Positive active material can promote the compacted density of iron manganese phosphate lithium compound, have high-energy density, high magnification, high/low temperature
The advantage of storage, and the safety problem that nickel cobalt manganese oxidate for lithium is brought can be solved.
To achieve the goals above, on the one hand, the present invention provides a kind of positive active material, which contains
There are nickel cobalt manganese oxidate for lithium and the iron manganese phosphate lithium compound shown in formula (1), the particle of the iron manganese phosphate lithium compound
The surface and the gap between the particle of the nickel cobalt manganese oxidate for lithium for being coated on the particle of the nickel cobalt manganese oxidate for lithium
In, the average grain diameter of the particle of the iron manganese phosphate lithium compound is 30-200nm；
LiMnxFe1-xPO4 (1)
Wherein, 0 ＜ x ＜ 1, preferably 0.5≤x≤0.8, more preferably 0.6≤x≤0.8.
On the other hand, the present invention also provides having given a kind of preparation method of above-mentioned positive active material, this method include with
Lower step：
(1) manganese salt, molysite, lithium salts, phosphoric acid and/or phosphate and nickel cobalt manganese oxidate for lithium are mixed in a solvent；
(2) in the presence of the first protective gas, the mixture that step (1) is mixed to get is atomized, is concentrated, is decomposed and
Crystallization.
The third aspect, the present invention also provides a kind of positive electrode of lithium ion battery, which contains above-mentioned
Positive active material and conductive agent.
Fourth aspect, the present invention also provides a kind of preparation method of the positive electrode of above-mentioned lithium ion battery, the party
Method includes：In the presence of the second protective gas, above-mentioned positive active material is mixed and is sintered with conductive agent.
5th aspect, the present invention also provides a kind of lithium ion battery, the anode of the lithium ion battery contains above-mentioned lithium
The positive electrode of ion battery.
According to the positive electrode of lithium ion battery provided by the invention, there is high-energy density and high safety performance.Contain
There is the lithium ion battery of above-mentioned positive electrode, there is high charge/discharge capacity, high energy bulk density and high safety performance.
According to the preparation method of positive active material provided by the invention, by manganese salt, molysite, lithium salts, phosphoric acid and/or phosphoric acid
After salt and nickel cobalt manganese oxidate for lithium mix in a solvent, then gained mixed solution is atomized, concentrated, decomposed and crystallized,
In obtained positive active material, manganese salt, molysite, lithium salts, phosphoric acid and/or phosphate can generate iron manganese phosphate lithium compound simultaneously
The surface of the particle of nickel cobalt manganese oxidate for lithium and embedded in the nickel cobalt manganese oxidate for lithium are coated on 30-200nm particle forms
In gap between grain.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the SEM figures of the positive active material in 1 positive electrode according to an embodiment of the invention.
Fig. 2 is the SEM figures of the positive active material in the positive electrode of comparative example 1 according to the present invention.
Fig. 3 is the positive active material (a) in 1 positive electrode and iron manganese phosphate for lithium used according to an embodiment of the invention
(b) and the XRD comparison diagrams of nickel cobalt manganese oxidate for lithium (c) used.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below in conjunction with attached drawing.It should be understood that this place is retouched
The specific implementation mode stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In the present invention, in the absence of explanation to the contrary, " average grain diameter " refers in 50,000 or 100,000 amplification factors
Under, the primary particle of random arbitrary 100 materials measures particle size values in SEM photograph, and average value is primary of the material
The average grain diameter of grain；" cladding " refers to all or part of table for being covered in nickel cobalt manganese oxidate for lithium of iron manganese phosphate lithium compound
Face；The crystal grain or the particle before amorphous particles reunion that " primary particle " refers to crystal grain.
The present invention provides a kind of positive active material, which contains nickel cobalt manganese oxidate for lithium and by formula
(1) iron manganese phosphate lithium compound shown in, the particles coat of the iron manganese phosphate lithium compound is in the nickel cobalt manganese oxidate for lithium
The surface of particle and the gap between the particle of the nickel cobalt manganese oxidate for lithium in, the iron manganese phosphate lithium compound
The average grain diameter of particle is 30-200nm；
LiMnxFe1-xPO4 (1)
Wherein, 0 ＜ x ＜ 1, preferably 0.5≤x≤0.8.
In the present invention, in order to further increase the performance of positive active material, in the manganese phosphate shown in formula (1)
In iron lithium compound, in the case of further preferred, 0.6≤x≤0.8.
In the present invention, the particle of the iron manganese phosphate lithium compound refers to primary of the iron manganese phosphate lithium compound
Grain, correspondingly, the average grain diameter of the particle of the iron manganese phosphate lithium compound refers to the primary of the iron manganese phosphate lithium compound
The average grain diameter of particle；The particle of the nickel cobalt manganese oxidate for lithium refers to the primary particle of the nickel cobalt manganese oxidate for lithium, accordingly
Ground, the average grain diameter of the particle of the nickel cobalt manganese oxidate for lithium refer to the average grain of the primary particle of the nickel cobalt manganese oxidate for lithium
Diameter.
According to the present invention, in the positive active material, the iron manganese phosphate lithium compound and the nickel cobalt manganese lithia
The content of compound can change in very large range, under preferable case, on the basis of the total weight of the positive active material, and institute
The content for stating iron manganese phosphate lithium compound is 1-99 weight %, and the content of the nickel cobalt manganese oxidate for lithium is 1-99 weight %.
Although the present invention can be realized in iron manganese phosphate lithium compound and nickel cobalt manganese oxidate for lithium containing above-mentioned content, in order to
The performance of the positive active material is further increased, in the case of further preferred, in the positive active material, with described
On the basis of the total weight of positive active material, the content of the iron manganese phosphate lithium compound is 20-50 weight %, the nickel cobalt manganese
The content of oxidate for lithium is 50-80 weight %.
In the present invention, the nickel cobalt manganese oxidate for lithium is not particularly limited, can be this field routinely makes
Nickel cobalt manganese oxidate for lithium, such as the nickel cobalt manganese oxidate for lithium can be as shown in formulas (2), LiNixCoyMnzO2(2),
In, x, y and z can meet：0 ＜ x ＜, 1,0 ＜ y ＜, 1,0 ＜ z ＜ 1, x+y+z=1, and x：y：Z=1-8：0.6-2：1.It is described
Nickel cobalt manganese oxidate for lithium is commercially available or adopts and is prepared by known method, as commercially available product, such as can be LiNi1/ 3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.8Co0.1Mn0.1O2Deng.
In the present invention, the average grain diameter of the particle of the nickel cobalt manganese oxidate for lithium is not particularly limited, it is excellent
In the case of choosing, the average grain diameter of the particle of the nickel cobalt manganese oxidate for lithium is 0.01-20 μm.
The present invention also provides a kind of preparation methods of above-mentioned positive active material, and this approach includes the following steps：
(1) manganese salt, molysite, lithium salts, phosphoric acid and/or phosphate and nickel cobalt manganese oxidate for lithium are mixed in a solvent；
(2) in the presence of the first protective gas, the mixture that step (1) is mixed to get is atomized, is concentrated, is decomposed and
Crystallization.
According to the present invention, for the manganese salt, molysite, lithium salts, phosphoric acid and/or phosphatic dosage, there is no special limits
It is fixed, as long as so that generating the iron manganese phosphate lithium compound formed shown in above-mentioned formula (1), such as the manganese salt, molysite, lithium salts
Can be 0.1-0.9 with the mole ratio of phosphoric acid and/or phosphatic dosage：0.1-0.9：1-1.05：1, under preferable case, institute
The molal quantity for stating manganese salt, molysite, lithium salts and phosphoric acid and/or phosphatic dosage is 0.5-0.8：0.2-0.5：1-1.03：1.
Under preferable case, dosage and manganese salt, molysite, lithium salts, phosphoric acid and/or phosphate and the nickel cobalt manganese lithium of the solvent
The weight ratio of the total dosage of oxide is 1-99：1.
According to method provided by the invention, the solvent is not particularly limited, as long as the solvent can be molten
Solve manganese salt, molysite, lithium salts, phosphoric acid and/or phosphate, preferably deionized water and/or ethyl alcohol, further preferably go from
Sub- water.
In the present invention, the mixing is not particularly limited, such as the manganese salt, molysite, lithium salts, phosphoric acid
And/or the process that phosphate and nickel cobalt manganese oxidate for lithium mix in a solvent can be：By the manganese salt, molysite, lithium salts, phosphorus
Acid and/or phosphate are dissolved in the solvent, then are mixed with nickel cobalt manganese oxidate for lithium.For the manganese salt, molysite, lithium salts and
The concentration that phosphoric acid and/or phosphate are dissolved in the solution that the solvent obtains is not particularly limited, such as in acquired solution
Manganese ion, iron ion/ferrous ion, lithium ion and phosphate radical total mol concentration can be 0.05-10mol/L, preferably
0.1-1mol/L。
In the present invention, for the mode of the mixing, also there is no particular limitation, can be commonly used in the art
Hybrid mode, such as emulsion dispersion, mechanical agitation, shearing, ball milling, husky mill and hypergravity etc..Under preferable case, the mixing
Mode is emulsion dispersion, and the emulsion dispersion can be carried out using emulsifying head, and there is no special for the rotating speed and time for emulsification
Restriction, as long as so that be uniformly dispersed, such as the rotating speed of emulsification can be 100-300000rpm, the time of the emulsification
Can be 1-120min.
In the present invention, in order to further increase the performance of positive active material, under preferable case, the nickel cobalt manganese lithia
The mole ratio of the dosage of compound and the dosage of the lithium salts is 0.9-1：1, further preferably 0.98-1：1.
According to method provided by the invention, the manganese salt can be manganese salt commonly used in the art, such as the manganese salt
Can be one or more in manganese nitrate, Mn nitrate, acetic acid Asia manganese and formic acid Asia manganese.
The molysite can be molysite commonly used in the art, such as the molysite can be ferric nitrate, ferrous nitrate,
It is one or more in ferrous acetate and formic acid ferrous iron.
The lithium salts can be lithium salts commonly used in the art, such as the lithium salts can be lithium hydroxide, lithium acetate,
It is one or more in lithium benzoate, lithium formate, lithium nitrate, lithium tartrate and lithium dihydrogen phosphate.
The phosphate can be one or more in lithium dihydrogen phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
The iron manganese phosphate lithium compound and the nickel cobalt manganese oxidate for lithium are consistent with above description, and details are not described herein.
In the present invention, in order to further increase positive active material, under preferable case, the atomization is so that step (1)
The mixture of gained is atomized into submicron order droplet.The mode of the atomization can be atomization side commonly used in the art
Formula, such as ultrasonic atomization, centrifugal atomizing or high pressure gas atomization etc., under preferable case, the mode of the atomization is using super
Sonic nebulizers carry out ultrasonic atomization.
According to method provided by the invention, the concentration, the process decomposed and crystallized can be including enrichment region, resolvers
It is carried out in the equipment of crystal region, such as U-shaped quartz ampoule.
In the present invention, the mixture obtained by step (1) is transferred to process that equipment is concentrated, decomposed and crystallized can
Think：The mixture obtained by step (1) is first atomized into droplet, then delivers droplets on to be sent in equipment by carrier gas and carries out
Concentration is decomposed and is crystallized.
The gas of the carrier gas can be one or more of nitrogen, argon gas and helium, under preferable case, the carrier
The hydrogen of 1-30 volumes % can also be contained.
In order to obtain better positive active material, the temperature of the concentration can be 100-300 DEG C, preferably 100-
200℃；The temperature of the decomposition can be 300-400 DEG C, preferably 320-360 DEG C；The temperature of the crystallization can be 400-
600 DEG C, preferably 480-560 DEG C.The concentration, the time decomposed and crystallized are not particularly limited, such as described
The time of concentration can be 0.01-60min；The time of the decomposition can be 0.01-60min；The time of the crystallization can be with
For 0.01-120min.
According to the method for the present invention, in step (1), it is described by manganese salt, molysite, lithium salts, phosphoric acid and/or phosphate and
The mixing of nickel cobalt manganese oxidate for lithium in a solvent can also carry out in the presence of complexing agent.The complexing agent enables to manganese ion
It can be evenly distributed in solution according to setting ratio well in dispersion with iron ion, it also can be simultaneously according to one when precipitation
Certainty ratio is precipitated out simultaneously.
The complexing agent can be complexing agent commonly used in the art, such as can be citric acid, sodium citrate, three second
It is one or more in hydramine and tartaric acid, preferably citric acid.
In the present invention, in step (2), first protective gas can be one kind in nitrogen, argon gas and helium
Or it is a variety of.
In order to further prevent ferrous ion or manganese ion to be aoxidized in preparation process or using trivalent iron salt when drops
The performance of low positive active material, under preferable case, the method further includes being passed through hydrogen in step (2), the hydrogen being passed through
Volume can be first protective gas volume 1-30%.
The present invention also provides a kind of positive electrode of lithium ion battery, which contains above-mentioned positive active material
And conductive agent.
In the case of, according to the invention it is preferred to, on the basis of the total weight of the positive electrode, the positive active material
Content is 90-99.5 weight %, further preferably 97-99 weight %；The content of the conductive agent is 0.5-10 weight %, into
One step is preferably 1-3 weight %.
In the present invention, conductive agent is not particularly limited, such as can is conduction commonly used in the art
Agent, if can positive electrode have good conductivity, such as the conductive agent can be electrically conductive graphite, carbon nanotube
With it is one or more in graphene.
The present invention also provides a kind of preparation method of the positive electrode of lithium ion battery, this method includes：It is protected second
It protects in the presence of gas, above-mentioned positive active material is mixed and dried with conductive agent.
According to the present invention, the mixing of the positive active material and conductive agent is not particularly limited.In order to make
It is better that the positive electrode performance more uniformly obtained must be mixed, under preferable case, by the positive active material and conductive agent
Dispersion is mixed in a solvent.Under preferable case, the dosage of the solvent is the 1-99 that weight is the positive active material
Times, more preferably 4-10 times.
According to the present invention, form is added for the conductive agent and is not particularly limited, such as the conductive agent can be with
It being added in the form of suspension, the suspension is distributed in solvent for the conductive agent and obtains mixture, under preferable case, institute
The solid content for stating suspension can be 0.1-50 weight %.
The solvent and mixed mode can be same as described above, and details are not described herein.
According to the present invention, the drying can be drying mode commonly used in the art, such as vacuum drying, indifferent gas
Body protects heat drying, spray drying, freeze-drying or expansion drying.When the positive active material and the conductive agent use
When dispersion is mixed in a solvent, the drying can be spray drying.
After the present inventor is the study found that mix and dry the positive active material with conductive agent, burnt
Knot can further increase the crystallinity of material, to further increase the performance of positive electrode, it is therefore preferable that in the case of, institute
The method of stating further includes being sintered after positive active material is mixed and dried with conductive agent.
In the present invention, the sintering is not particularly limited, such as the sintering can carry out in tube furnace, excellent
In the case of choosing, the condition of the sintering includes：The temperature of sintering is 400-600 DEG C, sintering time 8-12h.
According to the present invention, second protective gas can be one or more in nitrogen, argon gas and helium.
In the case of in the present invention, it is preferred to, the method further includes being passed through hydrogen during blending and sintering, is passed through
Hydrogen volume can be second protective gas volume 1-30%.
In addition, the present invention also provides a kind of lithium ion battery, the anode of the lithium ion battery contains above-mentioned positive electrode.Institute
The preparation method for stating lithium ion battery can be the preparation method of lithium ion battery of this field routine, such as the system of lithium ion battery
Preparation Method can be：The positive electrode, glue and SuperP are subjected to mixing dispersion in NMP, are then coated on smooth surface aluminium foil
On, then dried, be punched, tabletting etc. obtains the anode pole piece of lithium ion battery, then with the cathode of lithium ion battery, every
Film, electrolyte etc. make lithium ion battery.The glue, the cathode of lithium ion battery, electrolyte by those skilled in the art public affairs
Know, for example, the glue can be 5130 either 9100 cathode can be graphite or lithium metal piece, the electrolyte can be with
For LiPF6, it is one or more in EC and DEC.
The present invention will be described in detail by way of examples below.
In following embodiment：
Using S4800 (Hitachi, Ltd), test condition is for SEM tests：Voltage is 5kV, respectively in 5W, 10W and 15W multiple
Under take pictures.
Using D/max-2500 models (Rigaku), test condition is for XRD tests：Pipe pressure is 40kV, electric current is
200mA, step-length are 0.04 °, and test angle is 10 ° -90 °.
Embodiment 1
(1) by 114.21g manganese salts (four nitric hydrate Asia manganese, be purchased from Guangdong brilliance company), 70.52g molysite (six hydration nitre
Sour ferrous, be purchased from Guangdong brilliance company), 48.27g lithium salts (lithium nitrate is purchased from Guangdong brilliance company), 80.68g85% purity
Phosphoric acid (being purchased from Jiangmen Xing Wei companies) and 0.69g complexing agents (citric acid is purchased from Taishan Yue Qiao Reagent Companies) are dissolved in 2L deionizations
In water, the emulsified dispersions of 12000rpm 30 minutes.Then 386.24g nickel cobalt manganese oxidate for lithium is added into scattered solution
(LiNi0.5Co0.2Mn0.3O2, it is purchased from Shenzhen Zhenhua company), continue emulsion dispersion at 12000rpm 30 minutes.
(2) ultrasonic ultrasonic delay line memory and solution atomization is other small at submicron order is added in the mixture obtained step (1)
Then drop uses carrier gas (to contain 3%H2Argon gas) drop be transmitted in U-shaped quartz ampoule exist in the first protective gas (argon gas)
Under concentrated, decomposed and crystallized, the temperature of the concentration is 110 DEG C, and the time of concentration is 0.1min, the temperature of the decomposition
It is 360 DEG C, the time of the decomposition is 0.2min, and the temperature of the crystallization is 500 DEG C, and the time of the crystallization is 0.2min,
Positive active material A10 is obtained, wherein iron manganese phosphate lithium compound is LiMn0.65Fe0.35PO4。
(3) positive active material, the 40g solid contents obtained 80g steps (2) divides for 5% conductive agent (carbon nanotube)
It is dispersed in 500ml deionized waters, in the emulsified dispersions of 12000rpm 30 minutes, is then spray-dried, the powder after drying is existed
In 500 DEG C of tube furnaces, in the presence of the second protective gas (argon gas), Isothermal sinter 8 hours obtains positive material after natural cooling
Expect A1.
Embodiment 2
(1) by 86.5g manganese salts (acetic acid Asia manganese is purchased from Guangzhou brilliance company), 100.74g molysite (six nitric hydrates are ferrous,
Be purchased from Guangdong brilliance company), the phosphoric acid of 42.36g lithium salts (lithium hydroxide is purchased from Sichuan Xing Sheng companies), 69.16g85% purity
(being purchased from Jiangmen Xing Wei companies) and 0.66g complexing agents (citric acid is purchased from Taishan Yue Qiao Reagent Companies) are dissolved in 2L deionized waters,
The emulsified dispersions of 12000rpm 30 minutes.Then 96.56g nickel cobalt manganese oxidate for lithium is added into scattered solution
(LiNi0.5Co0.2Mn0.3O2, it is purchased from Shenzhen Zhenhua company), continue emulsion dispersion at 12000rpm 30 minutes.
(2) ultrasonic ultrasonic delay line memory and solution atomization is other small at submicron order is added in the mixture obtained step (1)
Then drop uses carrier gas (to contain 20%H2Argon gas) drop is transmitted in U-shaped quartz ampoule and is deposited in the first protective gas (argon gas)
It concentrated, decomposed and is crystallized under, the temperature of the concentration is 120 DEG C, and the time of concentration is 0.02min, the decomposition
Temperature is 320 DEG C, and time of the decomposition is 50min, and the temperature of the crystallization is 480 DEG C, and the time of the crystallization is
10min obtains positive active material A20, and wherein iron manganese phosphate lithium compound is LiMn0.5Fe0.5PO4。
(3) positive active material, the 60g solid contents obtained 100g steps (2) divides for 5% conductive agent (carbon nanotube)
It is dispersed in 500ml deionized waters, in the emulsified dispersions of 12000rpm 30 minutes, is then spray-dried, the powder after drying is existed
In 480 DEG C of tube furnaces, in the presence of the second protective gas (argon gas), Isothermal sinter 10 hours obtains anode after natural cooling
Materials A 2.
Embodiment 3
(1) by 115.98g manganese salts (formic acid Asia manganese is purchased from Guangdong brilliance company), (ferrous acetate is purchased from 34.79g molysite
Guangdong brilliance company), 48.27g lithium salts (lithium nitrate is purchased from Guangdong brilliance company), 92.02g ammonium hydrogen phosphates (be purchased from Guangdong brilliance
Company) and 0.52g complexing agents (citric acid is purchased from Taishan Yue Qiao Reagent Companies) be dissolved in 2L deionized waters, it is newborn under 12000rpm
Change dispersion 30 minutes.Then 179.33g nickel cobalt manganese oxidate for lithium (LiNi is added into scattered solution0.5Co0.2Mn0.3O2,
It is purchased from Shenzhen Zhenhua company), continue emulsion dispersion at 12000rpm 30 minutes.
(2) ultrasonic ultrasonic delay line memory and solution atomization is other small at submicron order is added in the mixture obtained step (1)
Then drop uses carrier gas (to contain 30%H2Argon gas) drop is transmitted in U-shaped quartz ampoule and is deposited in the first protective gas (argon gas)
It concentrated, decomposed and is crystallized under, the temperature of the concentration is 100 DEG C, and the time of concentration is 1min, the temperature of the decomposition
It it is 340 DEG C, the time of the decomposition is 10min, and the temperature of the crystallization is 560 DEG C, and the time of the crystallization is 60min, is obtained
To positive active material A30, wherein iron manganese phosphate lithium compound is LiMn0.8Fe0.2PO4。
(3) positive active material that obtains 110g steps (2), the conductive agent (electrically conductive graphite) that 61.6g solid contents are 5%
It is dispersed in 500ml deionized waters, in the emulsified dispersions of 12000rpm 30 minutes, is then spray-dried, by the powder after drying
In 560 DEG C of tube furnaces, in the presence of the second protective gas (argon gas), Isothermal sinter 12 hours obtains just after natural cooling
Pole materials A 3.
Embodiment 4
Positive electrode is prepared according to the method for embodiment 1, unlike, in step (2) and step (3) being passed through volume is
10% hydrogen of protective gas volume, step (2) obtain positive electrode active materials A40, and step (3) obtains positive electrode A4.
Embodiment 5
Positive electrode is prepared according to the method for embodiment 1, unlike, in step (3), the powder after spray drying is not
It is sintered, and directly obtains positive electrode A5.
Comparative example 1
(1) by 114.21g manganese salts (four nitric hydrate Asia manganese, be purchased from Guangdong brilliance company), 70.52g molysite (six hydration nitre
Sour ferrous, be purchased from Guangdong brilliance company), 48.27g lithium salts (lithium nitrate is purchased from Guangdong brilliance company), 80.68g85% purity
Phosphoric acid (being purchased from Jiangmen Xing Wei companies) and 0.69g complexing agents (citric acid is purchased from Taishan Yue Qiao Reagent Companies) are dissolved in 2L deionizations
In water, the emulsified dispersions of 12000rpm 30 minutes.
(2) mixture obtained step (1) is added in atomizer, is passed through, with ultrasonic ultrasonic delay line memory by solution atomization at
The other droplet of submicron order (contains 3%H with carrier gas2Argon gas) drop is transmitted in U-shaped quartz ampoule in protective gas (argon
Gas) in the presence of concentrated, decomposed and crystallized, the temperature of the concentration is 110 DEG C, and time of concentration is 0.1min, described point
The temperature of solution is 360 DEG C, and time of the decomposition is 0.2min, and the temperature of the crystallization is 500 DEG C, and the time of the crystallization is
0.2min obtains LiMn0.65Fe0.35PO4Material, then again by acquired LiMn0.65Fe0.35PO4Material and 386.24g nickel cobalt manganese lithiums
Oxide (LiNi0.5Co0.2Mn0.3O2, it is purchased from Shenzhen Zhenhua company) and it carries out being mixed to get positive active material D10, wherein phosphoric acid
Ferromanganese lithium compound is LiMn0.65Fe0.35PO4。
(3) positive active material, the 40g solid contents obtained 80g steps (2) divides for 5% conductive agent (carbon nanotube)
It is dispersed in 500ml deionized waters, in the emulsified dispersions of 12000rpm 30 minutes, is then spray-dried, the powder after drying is existed
In 500 DEG C of tube furnaces, in the presence of protective gas (argon gas), Isothermal sinter 8 hours obtains positive electrode after natural cooling
D1。
Comparative example 2
Positive electrode is prepared according to the method for embodiment 1, unlike, in step (1), it is lithium to be added without nickel cobalt manganese
Object, step (2) obtain positive active material D20, and step (3) obtains positive electrode D2.
Application Example 1
Using the positive electrode A1 that embodiment 1 obtains as the positive electrode of lithium ion battery, it is prepared into CR2025 buttons
Battery A11 and 053450 full battery A12, specifically, the process for preparing CR2025 button cells and 053450 full battery is：It will just
Pole active material, acetylene black, Kynoar (being purchased from Dongguan City Qing Feng plastic materials Co., Ltd, trade mark FR900) are by weight
Amount is than being 80：10：10 are dissolved in N-Methyl pyrrolidone, are coated on aluminium foil after stirring evenly, and dried at 110 DEG C ± 5 DEG C
It is roasting, obtain positive plate.Using metal lithium sheet as negative plate, diaphragm is microporous polypropylene membrane (Celgard 2300), and electrolyte is
The LiPF of 1.0mol/L6/ (EC+EMC+DMC) (wherein, LiPF6For lithium hexafluoro phosphate, EC is ethylene carbonate, and EMC is carbonic acid first
Ethyl ester, DMC are dimethyl carbonate, and the volume ratio of EC, EMC and DMC are 1：1：1) it, seals, makes in the glove box full of argon gas
At CR2025 button cells A11 and 053450 full battery A12.
Application Example 2-5 and Comparison study example 1-2
CR2025 button cells and 053450 full battery are prepared according to the method for Application Example 1, uses embodiment respectively
Positive electrode A2-A5 and D1-D2 in 2-5 and comparative example 1-2, obtain corresponding CR2025 button cells A21, A31, A41,
A51 and D11, D21 and 053450 full battery A22, A32, A42, A52 and D12, D22.
Test case
1, the material morphology object of positive active material is mutually tested
SEM is tested：The SEM figures that Fig. 1 is the positive active material A10 in the positive electrode of the embodiment of the present invention 1, Fig. 2
For the SEM figures of the positive active material D10 in the positive electrode of the comparative example 1 of the present invention.
In Fig. 1, bulky grain (average grain diameter is 0.2-6 μm) is nickel cobalt manganese oxidate for lithium primary particle, and little particle is (average
Grain size is 30-200nm) it is iron manganese phosphate for lithium primary particle.From Fig. 1, it is apparent that in the big of nickel cobalt manganese oxidate for lithium
Particle surface, which is grown, the little particle of a large amount of iron manganese phosphate for lithium, at the same the particle of the bulky grain of nickel cobalt manganese oxidate for lithium with
Also with the presence of the little particle of a large amount of iron manganese phosphate for lithium in gap between grain, the little particle of iron manganese phosphate for lithium is covered in well
The large particle surface of nickel cobalt manganese oxidate for lithium and be filled with nickel cobalt manganese oxidate for lithium bulky grain particle and particle between
Gap.Namely to be coated on nickel cobalt manganese lithium for particle form of the iron manganese phosphate for lithium in embodiment 1 with average grain diameter for 30-200nm
In the surface of the bulky grain of object and gap between the particle and particle of the bulky grain of the nickel cobalt manganese oxidate for lithium.And from figure
In 2 as can be seen that comparative example 1 in iron manganese phosphate for lithium and nickel cobalt manganese oxidate for lithium be all with average grain diameter be 0.2-5 μm two
Secondary ball or the mixing of aggregate form, iron manganese phosphate for lithium there is no by it is primary it is short grained in the form of to be grown in nickel, cobalt and manganese oxide big
The surface of particle is also not embedded in the gap between nickel, cobalt and manganese oxide bulky grain, nickel, cobalt and manganese oxide and phosphoric acid ferrimanganic
There are a large amount of gaps between lithium secondary ball.
XRD is tested：Fig. 3 is positive active material A10 (a) and phosphorus used in the positive electrode of the embodiment of the present invention 1
The XRD comparison diagrams of sour ferromanganese lithium (b) and nickel cobalt manganese oxidate for lithium (c) used.
From figure 3, it can be seen that the present invention positive electrode in positive active material still maintain iron manganese phosphate for lithium and
The independent characteristic peak of nickel cobalt manganese oxidate for lithium illustrates that there is no high-temperature fusions at one for iron manganese phosphate for lithium and nickel cobalt manganese oxidate for lithium
Phase.
2, electrochemical property test
CR2025 button cells A11, A21, A31, A41, the A51 respectively prepared by Application Example 1-5 and comparative example 1-2
Charge/discharge capacity test and multiplying power test are carried out with D11, D21, gained charge/discharge capacity, discharge-rate data are listed in Table 1 below.
Charge/discharge capacity is tested：At room temperature, CCCV is charged to 4.3V, cut-off current 0.01C under 0.1C multiplying powers, then
CC discharges into 2.5V under 0.1C multiplying powers；
Multiplying power is tested：CCCV is charged to 4.3V, cut-off current 0.01C under 0.1 multiplying power, then respectively in 1C, 2C, 5C and
CC discharges into 2.5V under 10C multiplying powers, and the ratio of the discharge capacity under each multiplying power and the discharge capacity of 0.1C multiplying powers is used as this times
Multiplying power efficiency under rate.
Table 1
3, security performance is tested
Under room temperature, by Application Example and 053450 full battery A12, A22, A32, A42, A52 of application comparative example
4.3 volts are charged to 1C milliamperes of electric currents respectively with D12, D22, with constant-potential charge, cut-off current after voltage rises to 4.3 volts
It is 0.05C milliamperes, shelves 5 minutes；Carry out 160 DEG C of stove Thermal tests, observation battery has without exception after 1h, and measures battery
The maximum temperature of the maximum temperature on surface, observation situation and battery surface to Examples and Comparative Examples is listed in Table 2 below.
Table 2
As can be seen from Table 1 and Table 2, higher compacted density and higher are had according to positive electrode provided by the invention
Energy density, the lithium ion battery containing the positive electrode is electrical with higher capacity and with superior charge and discharge
Energy and security performance.
The preferred embodiment of the present invention is described in detail above in association with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical scheme of the present invention
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (25)
1. a kind of positive active material, which is characterized in that the positive active material is by by manganese salt, molysite, lithium salts, phosphoric acid
And/or phosphate and nickel cobalt manganese oxidate for lithium mix in a solvent, and in the presence of the first protective gas, by what is be mixed to get
Obtained from mixture is atomized, is concentrated, is decomposed and is crystallized；Wherein, which contains nickel cobalt manganese oxidate for lithium
And the iron manganese phosphate lithium compound shown in formula (1), the particles coat of the iron manganese phosphate lithium compound is in the nickel cobalt manganese
In the surface of the particle of oxidate for lithium and gap between the particle of the nickel cobalt manganese oxidate for lithium, the iron manganese phosphate for lithium
The average grain diameter of the particle of compound is 30-200nm；
LiMnxFe1-xPO4 (1)
Wherein, 0 ＜ x ＜ 1.
2. positive active material according to claim 1, wherein 0.5≤x≤0.8.
3. positive active material according to claim 2, wherein 0.6≤x≤0.8.
4. positive active material according to claim 1, wherein on the basis of the total weight of the positive active material,
The content of the iron manganese phosphate lithium compound is 1-99 weight %, and the content of the nickel cobalt manganese oxidate for lithium is 1-99 weight %.
5. positive active material according to claim 4, wherein on the basis of the total weight of the positive active material,
The content of the iron manganese phosphate lithium compound is 20-50 weight %, and the content of the nickel cobalt manganese oxidate for lithium is 50-80 weights
Measure %.
6. positive active material according to claim 1, wherein the average grain diameter of the particle of the nickel cobalt manganese oxidate for lithium
It is 0.01-20 μm.
7. positive active material according to claim 6, wherein shown in the nickel cobalt manganese oxidate for lithium such as formula (2),
LiNixCoyMnzO2 (2)
Wherein, 0 ＜ x ＜, 1,0 ＜ y ＜, 1,0 ＜ z ＜ 1, x+y+z=1, and x：y：Z=1-8：0.6-2：1.
8. positive active material according to claim 1, wherein the manganese salt is manganese nitrate, Mn nitrate, acetic acid Asia manganese
With it is one or more in the manganese of formic acid Asia；
The molysite is one or more in ferric nitrate, ferrous nitrate, ferrous acetate and formic acid ferrous iron；
The lithium salts is in lithium hydroxide, lithium acetate, lithium benzoate, lithium formate, lithium nitrate, lithium tartrate and lithium dihydrogen phosphate
It is one or more；
The phosphate is one or more in lithium dihydrogen phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
9. positive active material according to claim 1, wherein the solvent is deionized water and/or ethyl alcohol.
10. positive active material according to claim 1, wherein the temperature of the concentration is 100-300 DEG C；
The temperature of the decomposition is 300-400 DEG C；
The temperature of the crystallization is 400-600 DEG C.
11. positive active material according to claim 10, wherein the temperature of the concentration is 100-200 DEG C；
The temperature of the decomposition is 320-360 DEG C；
The temperature of the crystallization is 480-560 DEG C.
12. the positive active material according to claim 10 or 11, wherein the concentration is decomposed and crystallized in U-shaped quartz
It is carried out in pipe.
13. positive active material according to claim 1, wherein described be blended in the presence of complexing agent carries out.
14. positive active material according to claim 13, wherein the complexing agent is citric acid, sodium citrate, three second
It is one or more in hydramine and tartaric acid.
15. positive active material according to claim 1, wherein first protective gas is nitrogen, argon gas and helium
In it is one or more.
16. positive active material according to claim 1, wherein under conditions of being passed through hydrogen, by the mixture into
Row atomization, is decomposed and is crystallized at concentration, and the 1-30% for the volume that the volume for the hydrogen being passed through is the first protective gas.
17. a kind of positive electrode of lithium ion battery, the positive electrode contain described in any one of claim 1-16 just
Pole active material and conductive agent.
18. positive electrode according to claim 17, wherein on the basis of the total weight of the positive electrode, it is described just
The content of pole active material is 90-99.5 weight %；The content of the conductive agent is 0.5-10 weight %.
19. positive electrode according to claim 18, wherein on the basis of the total weight of the positive electrode, it is described just
The content of pole active material is 97-99 weight %；The content of the conductive agent is 1-3 weight %.
20. positive electrode according to claim 17, wherein the conductive agent is electrically conductive graphite, carbon nanotube and graphite
It is one or more in alkene.
21. the preparation method of the positive electrode of the lithium ion battery described in any one of claim 17-20, this method packet
It includes：In the presence of the second protective gas, the positive active material described in any one of claim 1-16 is mixed with conductive agent
Merge drying.
22. according to the method for claim 21, wherein the method further includes being mixed by positive active material and conductive agent
It is sintered after merging drying.
23. according to the method for claim 21, wherein second protective gas is one in nitrogen, argon gas and helium
Kind is a variety of.
24. according to the method for claim 21, wherein the method further includes being passed through hydrogen during mixing and sintering
Gas, the volume for the hydrogen being passed through are the 1-30% of the volume of the second protective gas.
25. a kind of lithium ion battery, wherein the anode of the lithium ion battery contains described in any one of claim 17-20
Lithium ion battery positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410452137.0A CN105470495B (en) | 2014-09-05 | 2014-09-05 | The positive electrode and preparation method thereof and lithium ion battery of a kind of positive active material and preparation method thereof, lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410452137.0A CN105470495B (en) | 2014-09-05 | 2014-09-05 | The positive electrode and preparation method thereof and lithium ion battery of a kind of positive active material and preparation method thereof, lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105470495A CN105470495A (en) | 2016-04-06 |
| CN105470495B true CN105470495B (en) | 2018-09-11 |
Family
ID=55607989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410452137.0A Active CN105470495B (en) | 2014-09-05 | 2014-09-05 | The positive electrode and preparation method thereof and lithium ion battery of a kind of positive active material and preparation method thereof, lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105470495B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107546379B (en) * | 2017-08-18 | 2020-02-28 | 宁波致良新能源有限公司 | Lithium iron manganese phosphate-ternary material composite cathode material and preparation method thereof |
| CN108963200B (en) * | 2018-05-18 | 2021-10-29 | 浙江海创锂电科技有限公司 | Preparation and application of oxide-coated nitrided carbon nanotube-loaded nickel-cobalt-manganese positive electrode material |
| CN110400920A (en) * | 2019-07-05 | 2019-11-01 | 联动天翼新能源有限公司 | A kind of high-energy density long-life batteries and preparation method thereof |
| CN110459749B (en) * | 2019-08-21 | 2022-06-10 | 中国科学院宁波材料技术与工程研究所 | Composite cathode material 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 |
| CN112133900A (en) * | 2020-09-27 | 2020-12-25 | 上海华谊（集团）公司 | Positive electrode active material and lithium ion battery containing the same |
| CN114220968A (en) * | 2021-11-11 | 2022-03-22 | 荆门市格林美新材料有限公司 | Coated LiMn0.5Fe0.5PO4Lithium ion battery anode material and preparation method thereof |
| CN114203959B (en) * | 2021-12-13 | 2024-01-23 | 东莞新能安科技有限公司 | Electrode assembly, electrochemical device, and electronic device |
| CN114614006A (en) * | 2022-02-16 | 2022-06-10 | 深圳市贝特瑞纳米科技有限公司 | Composite cathode material, preparation method thereof and lithium ion battery |
| CN115832224B (en) * | 2023-01-05 | 2023-12-22 | 厦门海辰储能科技股份有限公司 | Positive plate and preparation method thereof, electrode assembly, energy storage device and electric equipment |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102738465B (en) * | 2012-07-20 | 2014-10-29 | 重庆大学 | Preparation method of lithium iron manganese phosphate cathode composite material |
| CN103178251B (en) * | 2013-03-15 | 2017-07-28 | 宁德新能源科技有限公司 | Lithium ion power battery cathode material and the lithium-ion-power cell comprising the material |
| CN103413944A (en) * | 2013-08-14 | 2013-11-27 | 宁波奈克斯特新材料科技有限公司 | Lithium manganese phosphate positive electrode material and preparation method thereof |
-
2014
- 2014-09-05 CN CN201410452137.0A patent/CN105470495B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105470495A (en) | 2016-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105470495B (en) | The positive electrode and preparation method thereof and lithium ion battery of a kind of positive active material and preparation method thereof, lithium ion battery | |
| US10957903B2 (en) | Layered lithium-rich manganese-based cathode material with olivine structured LIMPO4 surface modification and preparation method thereof | |
| Zhu et al. | Preparation of 4.7 áV cathode material LiNi0. 5Mn1. 5O4 by an oxalic acid-pretreated solid-state method for lithium-ion secondary battery | |
| JP5187520B2 (en) | Li-Ni composite oxide particle powder for non-aqueous electrolyte secondary battery, method for producing the same, and non-aqueous electrolyte secondary battery | |
| CN101188293B (en) | Fe base lithium sale compound anode materials and its making method | |
| Cao et al. | Synthesis and electrochemical performance of nanostructured LiMnPO4/C composites as lithium-ion battery cathode by a precipitation technique | |
| CN104752718B (en) | A kind of LiMnxFe1‑xPO4Positive electrode active materials and preparation method thereof | |
| US20190020015A1 (en) | Lithium manganese iron phosphate-based particulate for a cathode of a lithium battery, lithium manganese iron phosphate-based powdery material containing the same, and method for manufacturing the powdery material | |
| Lin et al. | The effects of quenching treatment and AlF3 coating on LiNi0. 5Mn0. 5O2 cathode materials for lithium-ion battery | |
| CN102185139A (en) | Preparation method of nanometer metallic oxide/graphene doped lithium iron phosphate electrode material | |
| KR20150080390A (en) | Positive electrode active material with improved energy density | |
| WO2005095273A1 (en) | Method for producing lithium-iron composite oxide | |
| CN102496714A (en) | Anode active substance, production method thereof, and lithium ion battery employing anode active substance | |
| CN105226273B (en) | A kind of iron manganese phosphate for lithium and preparation method and application | |
| JP2011134708A (en) | Particulate powder of positive active material for nonaqueous-electrolyte secondary battery and method of manufacturing the same, and nonaqueous-electrolyte secondary battery | |
| CN101794878A (en) | Method for preparing polyanionic lithium ion battery anode material | |
| CN102306791B (en) | Method for preparing carbon-cladding non-stoichiometric lithium iron phosphorous oxide material | |
| Fang et al. | Electrochemical properties of nano-and micro-sized LiNi0. 5Mn1. 5O4 synthesized via thermal decomposition of a ternary eutectic Li–Ni–Mn acetate | |
| CN104603061B (en) | Carbon applies the preparation method of lithium iron phosphate nano powder | |
| Xiang et al. | Improved electrochemical performance of Li1. 2Ni0. 2Mn0. 6O2 cathode material for lithium ion batteries synthesized by the polyvinyl alcohol assisted sol-gel method | |
| CN109037659A (en) | A kind of preparation method of bilayer carbon-coated LiFePO 4 for lithium ion batteries material | |
| Kong et al. | Synthesis and electrochemical performance of macroporous LiNi0. 5Co0. 2Mn0. 3O2 by a modified sol–gel method | |
| Huang et al. | Advanced Li-rich cathode collaborated with graphite/silicon anode for high performance Li-ion batteries in half and full cells | |
| Liu et al. | Synthesis of flower-like LiMnPO4/C with precipitated NH4MnPO4· H2O as precursor | |
| Lin et al. | One-step preparation of homogeneous single crystal Li-rich cathode materials with encouraging electrochemical performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |