CN104009233A - Method for improving performance of lithium manganate for lithium-ion battery - Google Patents

Method for improving performance of lithium manganate for lithium-ion battery Download PDF

Info

Publication number
CN104009233A
CN104009233A CN201410268731.4A CN201410268731A CN104009233A CN 104009233 A CN104009233 A CN 104009233A CN 201410268731 A CN201410268731 A CN 201410268731A CN 104009233 A CN104009233 A CN 104009233A
Authority
CN
China
Prior art keywords
lithium
ion
performance
limn2o4
solid content
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
Application number
CN201410268731.4A
Other languages
Chinese (zh)
Inventor
徐宁
赵明
吴孟涛
伏萍萍
宋英杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin B&M Science and Technology Co Ltd
Original Assignee
Tianjin B&M Science and Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tianjin B&M Science and Technology Co Ltd filed Critical Tianjin B&M Science and Technology Co Ltd
Priority to CN201410268731.4A priority Critical patent/CN104009233A/en
Publication of CN104009233A publication Critical patent/CN104009233A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a method for improving the performance of lithium manganate for a lithium-ion battery. The method comprises the steps that a raw material containing lithium ions, a raw material containing manganese ions and a raw material containing phosphate ions are prepared into water solutions respectively, lithium manganate to be treated is prepared into water suspensions in a normal-pressure reaction kettle, and then the lithium ion solution and the phosphate ion solution are poured into the normal-pressure reaction kettle in proportion to react through a metering pump; after the reaction, filtering and separation are conducted, so that solid matter is obtained, and the solid matter is washed; the obtained solid matter, water and polyhydric alcohol are prepared into a suspension, and the manganese ion solution is poured into the suspension at high temperature in a metered mode; after a reaction, filtering is conducted, so that solid matter is obtained and washed and dried; finally, the obtained solid matter is smashed, screened and packaged, and then the target product is obtained. According to the method for improving the performance of lithium manganate for the lithium-ion battery, the compatibility of lithium manganate with an electrolyte is improved through the wrapping method, the cycle performance, especially the high-temperature cycle performance, of lithium manganate is remarkably improved, the high-temperature self discharge ratio is lowered, and the high-temperature storage performance is improved.

Description

A kind of method that improves lithium-ion-power cell use LiMn2O4 performance
Technical field
The present invention relates to improving one's methods of a kind of anode material for lithium ion battery, particularly relate to a kind of method of lithium manganate material performance for lithium-ion-power cell that improves.
Background technology
Lithium ion battery is the secondary cell that a kind of energy density is high, merit metric density is high, the life-span is long, plays an important role in modern society.In the mini-plants such as mobile phone, notebook computer, lithium ion battery applications is very extensive.Meanwhile, along with the fast development of the industries such as electric automobile, intelligent grid, the demand of lithium-ion-power cell sharply rises, and its performance requirement is improved day by day.The positive electrode being applied in lithium ion battery is the deciding factor of its performance and cost.As anode material for lithium-ion batteries, LiMn2O4 has that operating voltage is high, electric discharge steadily, the advantage such as cost is low, fail safe is good, be highly suitable for lithium-ion-power cell system, be one of power type lithium-ion battery anode material of tool application prospect.Lithium manganate material is applied to lithium-ion-power cell, and the energy density that makes battery system is obtained to larger raising, and the amount of monomer of connecting under output voltage on the same group mutually reduces, and contributes to improve the reliability of battery pack, and the high power characteristic of battery pack is good.
Due to Jahn-Teller effect, in charge and discharge cycles process, the manganese oxygen octahedra structure of lithium manganate having spinel structure material internal unstable, adds the dissolving of bivalent manganese, causes material capacity decay fast, and cyclical stability is bad.When temperature rises, the performance of material can further worsen.And lithium-ion-power cell requires harsh to the high low temperature of material.For this reason, need to modify improvement to material.Common method of modifying has doping and coated.By doping, improve the comprehensive valence state of manganese in material, by the coated compatibility that improves material and electrolyte, finally improve the thermodynamics and kinetics stability of material, extend cycle life, widen the working temperature of material.The selection of dopant and covering is the work that will do on the one hand, on the other hand, also will select suitable method, makes doping and coated evenly reliable.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of employing normal pressure liquid phase reactor to carry out lithium phosphate to improved LiMn2O4 to be finished coated, then under normal pressure, coating layer carried out to the method for LiMn2O4 performance for the raising lithium-ion-power cell of manganese.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of method that improves lithium-ion-power cell use LiMn2O4 performance, comprises the following steps:
1) raw material containing lithium ion, manganese ion and phosphate anion is mixed with respectively to the aqueous solution;
2) in normal-pressure reaction kettle, pending LiMn2O4 is made to aqueous suspension, with measuring pump, lithium ion solution and phosphate anion solution are injected to normal-pressure reaction kettle in proportion and react, reacted rear isolated by filtration and obtained solid content, solid content is washed;
3) solid content obtaining and water, polyalcohol are mixed with to suspension-turbid liquid, under hot conditions, manganese ion solution is injected in metering, after having reacted, filters and obtains solid content, and it is washed, is dried;
4) the solid content product obtaining is pulverized, sieves, packed, obtain target product.
Described containing lithium ion be one or more in soluble salt and hydroxide containing the raw material of manganese ion, the raw material of phosphorus-containing acid ion is one or more in phosphoric acid and soluble phosphate.
By molal quantity, described raw material injection ratio is: n (PO 4 3+): n (LiMn 2o 4)=0.01-0.05, n (Mn 2+)=n (Li +)/3=1.05*n (PO 4 3-).
Described normal-pressure reaction kettle is with constant temperature and agitating device.
Described polyalcohol is one or more in the polyethylene glycol of ethylene glycol, glycerol and the degree of polymerization >=2.
Described pyroreaction temperature is 70-110 ℃, and the reaction time is 2-24h.
Described step 2) in, with deionized water, solid content is washed.
Described step 3) in, with deionized water, ethanol, solid content is washed successively.
The invention has the beneficial effects as follows: first, at the coated one deck lithium phosphate in lithium manganate particle surface to be finished, coating layer reacts with manganese ion and generates lithium manganese phosphate under relatively mild condition, obtains the coated LiMn2O4 of lithium manganese phosphate.After coated, improved the compatibility of LiMn2O4 and electrolyte, made its cycle performance, especially high temperature cyclic performance is significantly improved, and high temperature self-discharge rate declines, and high-temperature storage performance improves.
Accompanying drawing explanation
Fig. 1 is preparation method's of the present invention technological process.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail:
As shown in Figure 1, the method for LiMn2O4 performance for raising lithium-ion-power cell of the present invention, comprises the following steps:
1) raw material containing lithium ion, manganese ion and phosphate anion is mixed with respectively to the aqueous solution;
2) in normal-pressure reaction kettle, pending LiMn2O4 is made to aqueous suspension, with measuring pump, lithium ion solution and phosphate anion solution are injected to normal-pressure reaction kettle in proportion and react, reacted rear isolated by filtration and obtained solid content, solid content is washed;
3) solid content obtaining and water, polyalcohol are mixed with to suspension-turbid liquid, under hot conditions, manganese ion solution is injected in metering, after having reacted, filters and obtains solid content, and it is washed, is dried;
4) the solid content product obtaining is pulverized, sieves, packed, obtain target product.
Described containing lithium ion be one or more in soluble salt and hydroxide containing the raw material of manganese ion, the raw material of phosphorus-containing acid ion is one or more in phosphoric acid and soluble phosphate.
By molal quantity, described raw material injection ratio is: n (PO 4 3+): n (LiMn 2o 4)=0.01-0.05, n (Mn 2+)=n (Li +)/3=1.05*n (PO 4 3-).
Described normal-pressure reaction kettle is with constant temperature and agitating device.
Described polyalcohol is one or more in the polyethylene glycol of ethylene glycol, glycerol and the degree of polymerization >=2.
Described pyroreaction temperature is 70-110 ℃, and the reaction time is 2-24h.
Described step 2) in, with deionized water, solid content is washed.
Described step 3) in, with deionized water, ethanol, solid content is washed successively.
Embodiment 1
Prepare the following aqueous solution: 3.15moldm -3liOH solution, 1.00moldm -3h 3pO 4solution, 1.05moldm -3mnSO 4solution.In reactor, add 10dm 3deionized water and 2kg treat improved LiMn2O4, fully stir 35 ℃ of Temperature Settings.With measuring pump, add LiOH solution 111cm simultaneously 3and H 3pO 4solution 111cm 3.After having added, precipitation 30min.Filter, with deionized water washing precipitation 3 times.The solid content obtaining is transferred in reactor, added 5dm 3water-diethylene glycol (volume ratio 1:1) solution, after fully mixing, adds MnSO with measuring pump 4solution 111cm 3, at 70 ℃ of reaction 24h.Filter, with deionized water washing precipitation 4 times, with ethanol washing 1 time.After the solid content obtaining is dried, pulverize, sieve, obtain target product.
Embodiment 2
Prepare the following aqueous solution: 3.15moldm -3li 2sO 4solution, 2.00moldm -3(NH 4) 2hPO 4solution, 1.05moldm -3mn (NO 3) 2solution.In reactor, add 20dm 3deionized water and 3kg treat improved LiMn2O4, fully stir 35 ℃ of Temperature Settings.With measuring pump, add Li simultaneously 2sO 4solution 250cm 3(NH 4) 2hPO 4solution 250cm 3.After having added, precipitation 30min.Filter, with deionized water washing precipitation 3 times.The solid content obtaining is transferred in reactor, added 10dm 3water-glycerol (volume ratio 1:1) solution, after fully mixing, adds Mn (NO with measuring pump 3) 2solution 500cm 3, at 90 ℃ of reaction 15h.Filter, with deionized water washing precipitation 4 times, with ethanol washing 1 time.After the solid content obtaining is dried, pulverize, sieve, obtain target product.
Embodiment 3
Prepare the following aqueous solution: 3.15moldm -3cH 3cOOLi solution, 1.00moldm -3(NH 4) 3pO 4solution, 1.05moldm -3(CH 3cOO) 2mn solution.In reactor, add 50dm 3deionized water and 8kg treat improved LiMn2O4, fully stir 35 ℃ of Temperature Settings.With measuring pump, add CH simultaneously 3cOOLi solution 2220cm 3(NH 4) 3pO 4solution 2220cm 3.After having added, precipitation 30min.Filter, with deionized water washing precipitation 3 times.The solid content obtaining is transferred in reactor, added 15dm 3water-PEG400 (volume ratio 1:1) solution, after fully mixing, adds (CH with measuring pump 3cOO) 2mn solution 740cm 3, at 105 ℃ of reaction 5h.Filter, with deionized water washing precipitation 4 times, with ethanol washing 1 time.After the solid content obtaining is dried, pulverize, sieve, obtain target product.
Embodiment effect:
In sum, content of the present invention is not limited in the above-described embodiment, and the knowledgeable people in same area can propose easily other embodiment within technological guidance's thought of the present invention, but this embodiment comprises within the scope of the present invention.

Claims (8)

1. improve a method for LiMn2O4 performance for lithium-ion-power cell, it is characterized in that, comprise the following steps:
1) raw material containing lithium ion, manganese ion and phosphate anion is mixed with respectively to the aqueous solution;
2) in normal-pressure reaction kettle, pending LiMn2O4 is made to aqueous suspension, with measuring pump, lithium ion solution and phosphate anion solution are injected to normal-pressure reaction kettle in proportion and react, reacted rear isolated by filtration and obtained solid content, solid content is washed;
3) solid content obtaining and water, polyalcohol are mixed with to suspension-turbid liquid, under hot conditions, manganese ion solution is injected in metering, after having reacted, filters and obtains solid content, and it is washed, is dried;
4) the solid content product obtaining is pulverized, sieves, packed, obtain target product.
2. the method for LiMn2O4 performance for raising lithium-ion-power cell according to claim 1, it is characterized in that, described containing lithium ion be one or more in soluble salt and hydroxide containing the raw material of manganese ion, the raw material of phosphorus-containing acid ion is one or more in phosphoric acid and soluble phosphate.
3. the method for LiMn2O4 performance for raising lithium-ion-power cell according to claim 1, is characterized in that, by molal quantity, described raw material injection ratio is: n (PO 4 3+): n (LiMn 2o 4)=0.01-0.05, n (Mn 2+)=n (Li +)/3=1.05*n (PO 4 3-).
4. the method for LiMn2O4 performance for raising lithium-ion-power cell according to claim 1, is characterized in that, described normal-pressure reaction kettle is with constant temperature and agitating device.
5. the method for LiMn2O4 performance for raising lithium-ion-power cell according to claim 1, is characterized in that, described polyalcohol is one or more in the polyethylene glycol of ethylene glycol, glycerol and the degree of polymerization >=2.
6. the method for LiMn2O4 performance for raising lithium-ion-power cell according to claim 1, is characterized in that, described pyroreaction temperature is 70-110 ℃, and the reaction time is 2-24h.
7. the method for LiMn2O4 performance for raising lithium-ion-power cell according to claim 1, is characterized in that described step 2) in deionized water, solid content is washed.
8. the method for LiMn2O4 performance for raising lithium-ion-power cell according to claim 1, is characterized in that described step 3) in deionized water, ethanol, solid content is washed successively.
CN201410268731.4A 2014-06-17 2014-06-17 Method for improving performance of lithium manganate for lithium-ion battery Pending CN104009233A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410268731.4A CN104009233A (en) 2014-06-17 2014-06-17 Method for improving performance of lithium manganate for lithium-ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410268731.4A CN104009233A (en) 2014-06-17 2014-06-17 Method for improving performance of lithium manganate for lithium-ion battery

Publications (1)

Publication Number Publication Date
CN104009233A true CN104009233A (en) 2014-08-27

Family

ID=51369803

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410268731.4A Pending CN104009233A (en) 2014-06-17 2014-06-17 Method for improving performance of lithium manganate for lithium-ion battery

Country Status (1)

Country Link
CN (1) CN104009233A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102969482A (en) * 2012-12-10 2013-03-13 天津巴莫科技股份有限公司 Method for improving stability of anode material of lithium ion battery
CN103022485A (en) * 2012-12-19 2013-04-03 苏州大学 Lithium manganese phosphate-clad lithium manganate lithium secondary battery anode material and preparation method thereof
CN103700856A (en) * 2013-12-12 2014-04-02 天津巴莫科技股份有限公司 Preparation method of high-performance lithium manganese phosphate material for lithium-ion power batteries
KR20140064339A (en) * 2012-11-20 2014-05-28 주식회사 엘지화학 Method for preparation of olivine type lithium manganese phosphate and product obtained from the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140064339A (en) * 2012-11-20 2014-05-28 주식회사 엘지화학 Method for preparation of olivine type lithium manganese phosphate and product obtained from the same
CN102969482A (en) * 2012-12-10 2013-03-13 天津巴莫科技股份有限公司 Method for improving stability of anode material of lithium ion battery
CN103022485A (en) * 2012-12-19 2013-04-03 苏州大学 Lithium manganese phosphate-clad lithium manganate lithium secondary battery anode material and preparation method thereof
CN103700856A (en) * 2013-12-12 2014-04-02 天津巴莫科技股份有限公司 Preparation method of high-performance lithium manganese phosphate material for lithium-ion power batteries

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHI-LIU YANG ET. AL: ""Solvothermal synthesis of nano-LiMnPO4 from Li3PO4 rod-like precursor: reaction mechanism and electrochemical properties"", 《JOURNAL OF MATERIALS CHEMISTRY》 *

Similar Documents

Publication Publication Date Title
CN103682316B (en) The preparation method of long-life, high-capacity lithium ion cell tertiary cathode material
CN103855384B (en) A kind of ternary cathode material of lithium ion battery of rare-earth-doped modification and preparation method thereof
CN103928672B (en) A kind of positive electrode active material for lithium ion battery and preparation method thereof
US20200328406A1 (en) Layered lithium-rich manganese-based cathode material with olivine structured limpo4 surface modification and preparation method thereof
CN104710302B (en) Oxalic acid ferrimanganic presoma of grade doping and preparation method thereof
CN103500831B (en) Anion doped manganese based solid solution positive electrode and preparation method
CN104577088A (en) Lithium molybdate serving as secondary battery electrode material
CN102842711B (en) A kind of Zinc ferrite anode material of lithium ion battery and preparation method thereof and application
CN1785798A (en) Synthesis of lithium ion battery anode material vanadium lithium phosphate using sol-gel method
CN104037413A (en) Preparation method of positive electrode material (carbon-coated iron-manganese-lithium phosphate) of lithium ion battery
CN103390748B (en) A kind of preparation method of alumina-coated lithium cobaltate cathode material
CN103715416A (en) Preparation method for positive electrode material Li[Li0.201Ni0.133Co0.133Mn0.533]O2 of high-capacity lithium ion battery
CN102723480A (en) High-nickel-base lithium ion battery anode material and preparation method thereof
CN103178252A (en) Lithium ion battery anode material and preparation method thereof
CN105680050A (en) Battery anode material obtained by pyrolyzation of 2-methylimidazole zinc salt
CN105406071A (en) High-rate lithium vanadium phosphate positive electrode material, and preparation method and application thereof
CN102569724A (en) Preparation method for composite material used for anode of lithium ion battery
CN104051783A (en) Electrolyte for polyoxometallate ionic liquid lithium ion battery and preparation method of electrolyte
CN103700856B (en) The preparation method of high-performance lithium manganese phosphate material for lithium-ion-power cell
CN111916703B (en) In-situ synthesis method of lithium iron manganese phosphate/carbon@graphene composite material
CN108390050A (en) A kind of method for coating of lithium battery lithium manganate having spinel structure positive electrode
CN112103482A (en) Rare earth metal or transition metal doped lithium titanium phosphate/carbon composite material and preparation method and application thereof
CN102769134B (en) Preparation method of lithium ion battery anode composite material LiFePO4/C
WO2024055517A1 (en) Ferrophosphorus lithium-ion battery positive electrode material, and preparation method therefor and use thereof
CN109742375B (en) Surface layer recombined La2Ni0.5Li0.5O4And surface layer doped with La3+NCM ternary positive electrode material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into 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: 20140827