CN107732247A - A kind of lithium ion cell positive is material modified and preparation method thereof - Google Patents
A kind of lithium ion cell positive is material modified and preparation method thereof Download PDFInfo
- Publication number
- CN107732247A CN107732247A CN201711124107.7A CN201711124107A CN107732247A CN 107732247 A CN107732247 A CN 107732247A CN 201711124107 A CN201711124107 A CN 201711124107A CN 107732247 A CN107732247 A CN 107732247A
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- Prior art keywords
- lithium
- modified
- agi
- ion batteries
- cell positive
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- 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
It is material modified and preparation method thereof that the present invention discloses a kind of lithium ion cell positive, belongs to anode material for lithium-ion batteries technical field.The material modified positive pole is that anode material for lithium-ion batteries is modified using AgI, and specifically AgI is coated on positive electrode surface or bulk phase-doped modified to positive electrode progress, and the mol ratio of AgI and anode material for lithium-ion batteries is 0.001 0.2:1.The present invention is using AgI to anode material for lithium-ion batteries progress Surface coating and/or bulk phase-doped modified, so that clad is completely cutting off electrolyte with passing freely through lithium ion while positive electrode, the decomposition of electrolyte under high voltages is avoided while so as to complete discharge and recharge, improves high rate performance, cycle life and the stability of lithium ion battery.Material price used in the present invention is cheap, simple to operate, and technique is easily controllable.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries technical field, specifically a kind of lithium ion cell positive is material modified
And preparation method thereof.
Background technology
Lithium ion battery is due to operating voltage is high, energy density is big, have extended cycle life, have a safety feature, pollution-free
The advantages that and be widely used and pay close attention to.With going deep into for research, to the energy density of lithium ion battery, cycle performance and
Security performance etc. proposes higher requirement, and wherein positive electrode is the one of limiting lithium ion cell these aspect development
Individual principal element.
Chemical property earliest applied to the cobalt acid lithium material of industrialized production is more stable, and electric conductivity is preferable, follows
Ring performance is good, and especially compacted density can reach 4.0g/cm3, but its overcharge safety can be poor.Although LiMn2O4 has higher
Specific capacity, but structural stability is poor, the LiMn2O4 of nickel doping because have energy density corresponding to higher voltage platform compared with
Height, but the cycle performance under high temperature is poor, and ternary material has the advantages that heat endurance is good, energy density is high, but cyclicity
Energy, compacted density, security performance etc. are poor.
In order to improve the performance of positive electrode, conventional method be positive pole material surface is doped, Surface coating changes
Property.
The content of the invention
The defects of it is an object of the invention to overcome prior art to exist, there is provided a kind of lithium ion cell positive is material modified
And preparation method thereof, this method is modified using AgI to anode material for lithium-ion batteries, can be effectively improved positive electrode
Electric conductivity, high rate performance and cycle performance.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of lithium ion cell positive is material modified, and the material modified positive pole is to lithium ion cell positive using AgI
Material is modified, and the mol ratio of the AgI and anode material for lithium-ion batteries are 0.001-0.2:1.
Further scheme, the anode material for lithium-ion batteries be cobalt acid lithium, LiFePO4, lithium ferric manganese phosphate, LiMn2O4,
One or more of mixing in nickle cobalt lithium manganate, nickel cobalt lithium aluminate, lithium nickel cobalt dioxide or nickel ion doped.
It is of the invention that another purpose is to provide a kind of lithium ion cell positive material modified preparation method, it can pass through
Any one realization in following method：
(1) AgI materials are coated on anode material for lithium-ion batteries surface；
(2) AgI materials are carried out bulk phase-doped modified to anode material for lithium-ion batteries；
(3) AgI materials carry out bulk phase-doped modified to anode material for lithium-ion batteries and are coated on positive electrode table simultaneously
Face；
(4) AgI materials and anode material for lithium-ion batteries are adopted according to material modified stoichiometric proportion to be prepared
After making the two well mixed with solid phase method or liquid phase method, obtain lithium ion cell positive in atmosphere furnace high temperature solid-phase sintering and change
Property material；
(5) AgI is counted with the raw material for preparing anode material for lithium-ion batteries according to material modified chemistry to be prepared
It is material modified to obtain lithium ion cell positive than mixing by high temperature solid-phase sintering for amount.
Beneficial effects of the present invention：
(1) present invention is made using AgI to anode material for lithium-ion batteries progress Surface coating and/or bulk phase-doped modified
Clad avoids in isolation electrolyte with passing freely through lithium ion while positive electrode, while so as to complete discharge and recharge
The decomposition of electrolyte under high voltages, improve high rate performance, cycle life and the stability of lithium ion battery.
(2) material price used in the present invention is cheap, simple to operate, and technique is easily controllable.
Brief description of the drawings
Fig. 1 is charging and discharging curve figure under anode material for lithium-ion batteries different multiplying prepared by embodiment 1.
Fig. 2 is the 2C cycle charge-discharge curve maps of anode material for lithium-ion batteries prepared by embodiment 1.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Using lithium carbonate, nickel protoxide, mangano-manganic oxide as raw material, by LiNi0.5Mn1.5O4Middle Li, Ni, Mn stoichiometry
Than carrying out dispensing, after being well mixed, 900 DEG C of constant temperature 18h, and carry out 700 DEG C of annealing 24h in atmosphere.With LiNi0.5Mn1.5O4
For matrix, AgI is coated on LiNi0.5Mn1.5O4Blapharoplast surface, wherein AgI and LiNi0.5Mn1.5O4Mol ratio be 0.1:1,
The material modified composition of lithium ion cell positive is (LiNi0.5Mn1.5O4)·(AgI)0.1。
Embodiment 2
It is material modified by lithium ion cell positive to be prepared using lithium carbonate, manganese dioxide, AgI as raw material
(LiMn2O4)0.999·(AgI)0.001Stoichiometric proportion carry out dispensing, be well mixed after, 1000 DEG C of constant temperature in air atmosphere
24h, and 700 DEG C of annealing 24h are carried out, obtain the bulk phase-doped LiMn of AgI2O4 positive pole is material modified, wherein AgI and LiMn2O4's
Mol ratio is 1:999.
Embodiment 3
Using lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate, AgI as raw material, it is modified by lithium ion cell positive to be prepared
Material composition (LiFePO4)0.8·(AgI)0.2Stoichiometric proportion carry out dispensing, be well mixed after, 1000 in nitrogen atmosphere
DEG C constant temperature 24h, obtains the bulk phase-doped LiFePO of AgI4Positive electrode, wherein AgI and LiFePO4Mol ratio be 1:4.
Embodiment 4
AgI is distributed in ethanol, lithium ferric manganese phosphate is added in the solution, after being well mixed, heating evaporation to shape
Into powder, it is material modified to obtain lithium ferric manganese phosphate-iodate silver positive electrode, wherein, the mol ratio of silver iodide and lithium ferric manganese phosphate is
0.1:1。
Embodiment 5
The present disclosure applies equally to the cladding and/or doping of other anode material for lithium-ion batteries and AgI fast-ionic conductors
It is modified, such as lithium ferric manganese phosphate, nickel cobalt lithium aluminate, cobalt acid lithium or nickle cobalt lithium manganate.
Comparative example 1
The difference of comparative example 1 and embodiment 1 is：Uncoated LiNi0.5Mn1.5O4Material.
Lithium ion cell positive prepared by embodiment 1 is material modified electric using indigo plant with the electrochemical property test of comparative example 1
Battery test system is tested at room temperature.Cycle performance test condition：Test voltage scope is 3.5V-4.9V, with 0.2C,
1C, 2C, 3C, 5C discharge and recharge, discharge and recharge then is carried out in 2C multiplying powers, circulated 200 weeks.As shown in figure 1, uncoated material is in 0.2C
Specific discharge capacity under multiplying power is 128.5mAh/g, and the specific discharge capacity under 1C multiplying powers is 128.1mAh/g, putting under 2C multiplying powers
Electric specific capacity is 127.3mAh/g, and the specific discharge capacity under 3C multiplying powers is 126.5mAh/g, and the specific discharge capacity under 5C multiplying powers is
125.4mAh/g。(LiNi0.5Mn1.5O4)·(AgI)0.1The material modified specific discharge capacity under 0.2C multiplying powers is 128.9mAh/
Specific discharge capacity under g, 1C multiplying power is 128.8mAh/g, and the specific discharge capacity under 2C multiplying powers is 128.5mAh/g, under 3C multiplying powers
Specific discharge capacity be 128.1mAh/g, the specific discharge capacity under 5C multiplying powers is 127.6mAh/g.As shown in Fig. 2 2C electric discharges follow
The capability retention of 200 weeks uncoated materials of ring be 85.3%, and modified material be more than 96.8%, cycle performance is changed
It is kind.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.Person skilled in the art obviously can easily make various modifications to case study on implementation, and described herein one
As principle be applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation case here
Example, for those skilled in the art according to the announcement of the present invention, not departing from improvement that scope made and modification all should be
Within protection scope of the present invention.
Claims (3)
1. a kind of lithium ion cell positive is material modified, it is characterised in that the material modified positive pole is to lithium ion using AgI
Cell positive material is modified, and the mol ratio of the AgI and anode material for lithium-ion batteries are 0.001-0.2:1.
2. lithium ion cell positive according to claim 1 is material modified, it is characterised in that the lithium ion cell positive
Material is cobalt acid lithium, LiFePO4, lithium ferric manganese phosphate, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, lithium nickel cobalt dioxide or nickel manganese
One or more of mixing in sour lithium.
3. the material modified preparation method of lithium ion cell positive as claimed in claim 1, it is characterised in that can be by as follows
Any one realization in method：
（1）AgI materials are coated on anode material for lithium-ion batteries surface；
（2）AgI materials carry out bulk phase-doped modified to anode material for lithium-ion batteries；
（3）AgI materials carry out bulk phase-doped modified to anode material for lithium-ion batteries and are coated on positive electrode surface simultaneously；
（4）By AgI materials and anode material for lithium-ion batteries according to material modified stoichiometric proportion to be prepared, using solid
After phase method or liquid phase method make the two well mixed, obtain lithium ion cell positive in atmosphere furnace high temperature solid-phase sintering and be modified material
Material；
（5）By AgI and the raw material of anode material for lithium-ion batteries is prepared according to material modified stoichiometric proportion to be prepared
Mixing, it is material modified to obtain lithium ion cell positive by high temperature solid-phase sintering.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101673822A (en) * | 2009-09-24 | 2010-03-17 | 福建师范大学 | Preparation method of lithium iron phosphate cathode material simultaneously blended with silver and iodine |
| CN101847717A (en) * | 2010-05-27 | 2010-09-29 | 合肥工业大学 | Preparation method of lithium titanate composite negative electrode materials used by lithium ion batteries |
| CN104011918A (en) * | 2011-10-26 | 2014-08-27 | 耐克森有限公司 | Electrode composition for secondary battery cell |
| CN105304905A (en) * | 2015-09-23 | 2016-02-03 | 合肥国轩高科动力能源有限公司 | Modified material for positive electrode of lithium ion battery and preparation method of modified material |
-
2017
- 2017-11-14 CN CN201711124107.7A patent/CN107732247A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101673822A (en) * | 2009-09-24 | 2010-03-17 | 福建师范大学 | Preparation method of lithium iron phosphate cathode material simultaneously blended with silver and iodine |
| CN101847717A (en) * | 2010-05-27 | 2010-09-29 | 合肥工业大学 | Preparation method of lithium titanate composite negative electrode materials used by lithium ion batteries |
| CN104011918A (en) * | 2011-10-26 | 2014-08-27 | 耐克森有限公司 | Electrode composition for secondary battery cell |
| CN105304905A (en) * | 2015-09-23 | 2016-02-03 | 合肥国轩高科动力能源有限公司 | Modified material for positive electrode of lithium ion battery and preparation method of modified material |
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