CN104900904A - Lithium ion secondary battery - Google Patents

Lithium ion secondary battery Download PDF

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Publication number
CN104900904A
CN104900904A CN201510269887.9A CN201510269887A CN104900904A CN 104900904 A CN104900904 A CN 104900904A CN 201510269887 A CN201510269887 A CN 201510269887A CN 104900904 A CN104900904 A CN 104900904A
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China
Prior art keywords
nmp
pvdf
lithium
super
lini
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CN201510269887.9A
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Chinese (zh)
Inventor
彭卓
刘恩新
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Shenzhen Season Energy Technology Ltd
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Shenzhen Season Energy Technology Ltd
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Priority to CN201510269887.9A priority Critical patent/CN104900904A/en
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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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/5805—Phosphides
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/5835—Comprising fluorine or fluoride salts
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a lithium ion secondary battery which comprises a positive plate and a negative plate, wherein the positive plate is prepared from mixture of modified nickel-cobalt binary (LiNiXCoYW<1-X-Y>O2) and modified lithium iron phosphate(LiFeXR<1-X>PO4), graphitized carbon black (Super-P), conductive graphite (KS-6), polyvinylidene fluoride binder (PVDF) and 1-methyl-2-pyrrolidinone (NMP), the mixture of modified nickel-cobalt binary (LiNiXCoYW<1-X-Y>O2) and modified lithium iron phosphate(LiFeXR<1-X>PO4) is marked as (LiNiXCoYW<1-X-Y>O2+LiFeXR<1-X>PO4), the mass ratio of (LiNiXCoYW<1-X-Y>O2+LiFeXR<1-X>PO4) to Super-P to KS-6 to PVDF to NMP is (90-93) to (3-4) to 1 to (3-5) to 100, the mass ratio of LiNiXCoYW<1-X-Y>O2 to LiFeXR<1-X>PO4 is any one of 4 to 6, 5 to 5, 6 to 4, 7 to 3, and 8 to 2, in LiNiXCoYW<1-X-Y>O2, X is within the range of 0.4-0.8, Y is within the range of 0-0.6, W is any one of Zr, Al, Mg, Mn, Ti and Cr, in LiFeXR<1-X>PO4, X is within the range of 0.5-1, R is any one of Ni, Mg, Mn, Co, Ti and Cr.

Description

A kind of lithium rechargeable battery
Technical field
The present invention relates to lithium rechargeable battery, especially a kind of special material formula of lithium rechargeable battery.
Background technology
At present; lithium battery technology is tending towards ripe gradually, and various countries greatly develop electric automobile, solves day by day poor petroleum fuel gas resource on the one hand; solve natural environment be on the other hand subject to brokenly the sense of crisis of ring and increase severely day, therefore the domestic and international research to large doubly forthright lithium rechargeable battery also constantly heats up.Current governmental input fund energetically, carrys out Development of EV, lithium rechargeable battery as electric automobile critical component, one of its charging interval oversize main restrictive condition always becoming power vehicle wide popularization and application.
For lithium rechargeable battery, the design changing inside battery is the main path improving high rate discharge for lithium ion battery, electrode active material and conductive agent, the proportioning of binding agent, the high-rate discharge ability tool of the surface density of electrode slice to lithium ion battery have a great impact, therefore, at present the improvement of the preparation technology of lithium battery is brought into schedule.And lithium rechargeable battery of going together at present fails to accomplish good ratio optimization to pole piece material, generally need just can be full of for 2-4 hour 90% electricity, its charging interval still can not well satisfy the demand.
Summary of the invention
Therefore, for above-mentioned problem, the present invention proposes a kind of lithium rechargeable battery, and adopt unique positive and negative pole material formula, the quick charge making electrokinetic cell 20min be full of the electricity of 90% becomes possibility.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme: a kind of lithium rechargeable battery, comprises positive plate and negative plate, and wherein, positive plate forms according to following recipe configuration: positive plate comprises Modified Nickel cobalt binary (LiNi xco yw 1-X-Yo 2) and modified phosphate iron lithium (LiFe xr 1-XpO 4) mixture, conductive black (Super-P), electrically conductive graphite (KS-6), Kynoar binding agent (PVDF) and nitrogen methyl pyrrolidone solvent (NMP), the mixture of Modified Nickel cobalt binary and modified phosphate iron lithium is designated as (LiNi xco yw 1-X-Yo 2+ LiFe xr 1-XpO 4).The proportioning of above-mentioned material is: (LiNi xco yw 1-X-Yo 2+ LiFe xr 1-XpO 4): the mass ratio of Super-P:KS-6:PVDF:NMP is (90-93): (3-4): 1:(3-5): 100; Wherein, LiNi xco yw 1-X-Yo 2: LiFe xr 1-XpO 4choose 4:6,5:5,6:4,7:3,8:2 wherein any one, LiNi xco yw 1-X-Yo 2in X to choose interval be [0.4-0.8], Y to choose interval be [0-0.6], W is any one in Zr, Al, Mg, Mn, Ti and Cr; LiFe xr 1-XpO 4middle X to choose interval be [0.5-1], R is Ni, Mg, Mn, Co, any one in Ti and Cr.
Preferably, (LiNi xco yw 1-X-Yo 2+ LiFe xr 1-XpO 4): the proportioning of Super-P:KS-6:PVDF:NMP is 93:3:1:3:100.
Negative plate forms according to following recipe configuration: negative plate comprises active material lithium electricity charcoal element (C), conductive black (Super-P), CNT (carbon nano-tube) conductive agent (CNT), Kynoar binding agent (PVDF) and nitrogen methyl pyrrolidone solvent (NMP), and its proportioning is as follows: the mass ratio of C:Super-P:CNT:PVDF:NMP is (90-93): (3-4): 1:(3-5): 100.
Wherein, positive negative film manufacture craft is as follows: Kynoar binding agent (PVDF) and nitrogen methyl pyrrolidone solvent (NMP) are mixed according to mass ratio 5:95-7:93, stir with lithium electricity mixer and stirred for 3 hours, add Modified Nickel cobalt binary and modified phosphate iron lithium mixture again, continue stirring and stirred for 5 hours.
The manufacture craft of negative plate is as needed: first Kynoar binding agent (PVDF) and nitrogen methyl pyrrolidone solvent (NMP) are mixed according to mass ratio 5:95-7:93, stir with lithium electricity mixer and stirred for 3 hours, add CNT (carbon nano-tube) conductive agent (CNT) dispersion liquid again, continue stirring 1 hour, after add conductive black (Super-P) and stir 1 hour again, finally add lithium electricity charcoal element (C), after adding nitrogen methyl pyrrolidone solvent (NMP) adjusting viscosity, continue stirring 4 hours.
Present invention employs above-mentioned formula, by the formulation optimization of positive level sheet and negative plate, the large multiplying power charging performance of Soft Roll lithium electric power battery is significantly promoted, and the charging interval significantly shortens.
Embodiment
Now in conjunction with embodiment, the present invention is further described.
Lithium rechargeable battery special material formula provided by the invention comprises the material prescription of positive plate and the material prescription of negative plate.The material prescription of positive plate comprises active material Modified Nickel cobalt manganese binary (LiNi xco yw 1-X-Yo 2) and modified phosphate iron lithium (LiFe xr 1-XpO 4) this mixture (is designated as: (LiNi by mixture xco yw 1-X-Yo 2+ LiFe xr 1-XpO 4)), conductive black (Super-P), electrically conductive graphite (KS-6), Kynoar binding agent (PVDF), and nitrogen methyl pyrrolidone solvent (NMP); The material prescription of negative plate comprises active material lithium electricity charcoal element (C), conductive black (Super-P), CNT (carbon nano-tube) conductive agent (CNT), Kynoar binding agent (PVDF), and nitrogen methyl pyrrolidone solvent (NMP).
Wherein, the formula of positive plate is (LiNi xco yw 1-X-Yo 2+ LiFe xr 1-XpO 4): Super-P:KS-6:PVDF:NMP=93:3:1:3:100 (between 93:3:1:3:100-90:4:1:5:100, the present invention chooses 93:3:1:3:100 to mass ratio), LiNi xco yw 1-X-Yo 2: LiFe xr 1-XpO 4mass ratio be 4:6, any one in 5:5,6:4,7:3 or 8:2, concrete proportioning can be determined according to user's request and battery volumetric specific energy, wherein, the formula fail safe of 4:6 is higher, but volumetric specific energy is relatively lower, the formula volumetric specific energy of 8:2 is higher, but relative safety is more weak, but prove through many experiments, said ratio all can meet existing rower requirement.LiNi xco yw 1-X-Yo 2) X=0.4-0.8, Y=0-0.6, W are Zr, Al, Mg, Mn, Cr wherein any one, and at LiFe xr 1-XpO 4middle X=0.5-1, R are Ni, Mg, Mn, Co, Cr wherein any one.Specific embodiments is as follows: first Kynoar binding agent (PVDF) and nitrogen methyl pyrrolidone solvent (NMP) are mixed according to mass ratio 5:95-7:93,3 hours are stirred with lithium electricity mixer, add Modified Nickel cobalt binary and modified phosphate iron lithium mixture again, continue stirring 5 hours.
The material prescription of negative plate is C:Super-P:CNT:PVDF:NMP=93:3:1:3:100, C can be Delanium, native graphite, MCMB, hard carbon, soft carbon, any one in the materials such as composite graphite.Specific embodiments is as follows: first Kynoar binding agent (PVDF) and nitrogen methyl pyrrolidone solvent (NMP) are mixed according to mass ratio 5:95-7:93,3 hours are stirred with lithium electricity mixer, add CNT (carbon nano-tube) conductive agent (CNT) dispersion liquid again, continue stirring 1 hour, after add conductive black (Super-P) and stir 1 hour again, finally add lithium electricity charcoal element (C), after adding nitrogen methyl pyrrolidone solvent (NMP) adjusting viscosity, continue stirring 4 hours.
The contrast table of the main positive electrode of current lithium electricity is as follows:
In the main positive electrode of current lithium electricity, simple cobalt acid lithium gram volume (gram volume: every gram of lithium electric material is containing how many mAh (MAH) electricity, its unit is: mAh/g (MAH every gram)) medium, only has about 140-150mAh/g, and in cyclic process, because the position capacity of cobalt is occupied by other ions, crystal structure easily changes; Simple iron lithium material, current gram volume only has 130mAh/g, but security performance is good, Stability Analysis of Structures; Simple nickel cobalt binary, gram volume is up to arriving 180mAh/g, but fail safe is poor; , in charge and discharge process, easily there is disproportionated reaction in simple lithium manganate material, crystal structure is unstable, and gram volume is also low, only has 110mAh/g, but security performance is better.
And in the present invention, its formula adopts Modified Nickel cobalt binary material, LiNi in Modified Nickel cobalt binary material xco yo 2itself there is higher gram volume, and the phase transformation that inhibit material in charging process that a small amount of modifying element W that adulterates plays, thus improve the performance of fail safe and large current charge; In LiFePO4, strong P-O covalent bond itself forms the three-dimensional stereochemistry key of delocalization, make LiFePO4 have very strong thermodynamics and kinetics to stablize, security performance is better, Stability Analysis of Structures, in cyclic process, crystal structure is not easy change, and after R ion doping, electronic conductivity increases, and makes its charge-discharge performance from further enhancing.On the whole, remodeling nickel cobalt binary capacity can promote the capacity of formula, remodeling LiFePO4 can take into account its rapid charge characteristic and security performance, formula capacity is made to reach 170-175mAh/g, and have 5C large current charge and good security performance concurrently, thus reach 20min and fill 90% and become possibility.
Present invention employs above-mentioned formula, the present invention is optimized by anode formula, and the large multiplying power charging performance of Soft Roll lithium electric power battery is significantly promoted, and the charging interval significantly shortens.The battery of lithium rechargeable battery of the present invention and prior art contrasts as follows:
Rapid charge characteristic Repid discharge performance
Lithium rechargeable battery of the present invention Within 20 minutes, be full of 90% electricity Maximum 300A electric discharge
Existing general polymer battery Within 2-4 hour, be full of 90% electricity 20A discharges
Although specifically show in conjunction with preferred embodiment and describe the present invention; but those skilled in the art should be understood that; not departing from the spirit and scope of the present invention that appended claims limits; can make a variety of changes the present invention in the form and details, be protection scope of the present invention.

Claims (6)

1. a lithium rechargeable battery, comprises positive plate and negative plate, and wherein, positive plate forms according to following recipe configuration: positive plate comprises Modified Nickel cobalt binary (LiNi xco yw 1-X-Yo 2) and modified phosphate iron lithium (LiFe xr 1-XpO 4) mixture, conductive black (Super-P), electrically conductive graphite (KS-6), Kynoar binding agent (PVDF) and nitrogen methyl pyrrolidone solvent (NMP), the mixture of Modified Nickel cobalt binary and modified phosphate iron lithium is designated as (LiNi xco yw 1-X-Yo 2+ LiFe xr 1-XpO 4);
(LiNi xco yw 1-X-Yo 2+ LiFe xr 1-XpO 4): the mass ratio of Super-P:KS-6:PVDF:NMP is (90-93): (3-4): 1:(3-5): 100;
W is any one in Zr, Al, Mg, Mn, Ti and Cr;
R is Ni, Mg, Mn, Co, any one in Ti and Cr.
2. lithium rechargeable battery according to claim 1, is characterized in that: LiNi xco yw 1-X-Yo 2in X to choose interval be [0.4-0.8], Y to choose interval be [0-0.6].
3. lithium rechargeable battery according to claim 1 and 2, is characterized in that: LiFe xr 1-XpO 4middle X chooses interval for [0.5-1].
4. lithium rechargeable battery according to claim 1, is characterized in that: LiNi xco yw 1-X-Yo 2: LiFe xr 1-XpO 4choose 4:6,5:5,6:4,7:3,8:2 wherein any one.
5. lithium rechargeable battery according to claim 1, is characterized in that: (LiNi xco yw 1-X-Yo 2+ LiFe xr 1-XpO 4): the mass ratio of Super-P:KS-6:PVDF:NMP is 93:3:1:3:100.
6. lithium rechargeable battery according to claim 1, it is characterized in that: negative plate comprises active material lithium electricity charcoal element (C), conductive black (Super-P), CNT (carbon nano-tube) conductive agent (CNT), Kynoar binding agent (PVDF) and nitrogen methyl pyrrolidone solvent (NMP), and its proportioning is as follows: the mass ratio of C:Super-P:CNT:PVDF:NMP is (90-93): (3-4): 1:(3-5): 100.
CN201510269887.9A 2015-05-25 2015-05-25 Lithium ion secondary battery Pending CN104900904A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106169559A (en) * 2016-08-01 2016-11-30 山东威能环保电源科技股份有限公司 A kind of cathode size, the preparation method of cathode size and use the negative plate and lithium ion battery that this cathode size makes
CN112582604A (en) * 2020-03-18 2021-03-30 新余学院 Modification method of high-nickel ternary lithium battery positive electrode material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101436654A (en) * 2007-11-13 2009-05-20 深圳市慧通天下科技股份有限公司 Ferric phosphate lithium type safety high power lithium ion battery
CN102386409A (en) * 2011-11-03 2012-03-21 湖南丰源业翔晶科新能源股份有限公司 Paste for cathode of lithium iron phosphate lithium ion battery
CN104577012A (en) * 2014-12-29 2015-04-29 山东精工电子科技有限公司 Rate cycling improved lithium iron phosphate battery and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101436654A (en) * 2007-11-13 2009-05-20 深圳市慧通天下科技股份有限公司 Ferric phosphate lithium type safety high power lithium ion battery
CN102386409A (en) * 2011-11-03 2012-03-21 湖南丰源业翔晶科新能源股份有限公司 Paste for cathode of lithium iron phosphate lithium ion battery
CN104577012A (en) * 2014-12-29 2015-04-29 山东精工电子科技有限公司 Rate cycling improved lithium iron phosphate battery and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106169559A (en) * 2016-08-01 2016-11-30 山东威能环保电源科技股份有限公司 A kind of cathode size, the preparation method of cathode size and use the negative plate and lithium ion battery that this cathode size makes
CN112582604A (en) * 2020-03-18 2021-03-30 新余学院 Modification method of high-nickel ternary lithium battery positive electrode material

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