CN108470905A - LiFePO4 adulterates ternary positive electrode active material, lithium ion battery and preparation method thereof - Google Patents
LiFePO4 adulterates ternary positive electrode active material, lithium ion battery and preparation method thereof Download PDFInfo
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- CN108470905A CN108470905A CN201810170851.9A CN201810170851A CN108470905A CN 108470905 A CN108470905 A CN 108470905A CN 201810170851 A CN201810170851 A CN 201810170851A CN 108470905 A CN108470905 A CN 108470905A
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- positive electrode
- lifepo4
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- 229910052493 LiFePO4 Inorganic materials 0.000 title claims abstract description 60
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 72
- 239000006258 conductive agent Substances 0.000 claims description 25
- 239000011883 electrode binding agent Substances 0.000 claims description 25
- 239000007773 negative electrode material Substances 0.000 claims description 15
- 229910021385 hard carbon Inorganic materials 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 229910021384 soft carbon Inorganic materials 0.000 claims description 9
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 229910021382 natural graphite Inorganic materials 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910012748 LiNi0.5Mn0.3Co0.2O2 Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 210000004779 membrane envelope Anatomy 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 12
- 229910052744 lithium Inorganic materials 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000005955 Ferric phosphate Substances 0.000 description 9
- 229940032958 ferric phosphate Drugs 0.000 description 9
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 9
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 239000002174 Styrene-butadiene Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000006182 cathode active material Substances 0.000 description 3
- 229920006184 cellulose methylcellulose Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 2
- ZSYNKHJUSDFTCQ-UHFFFAOYSA-N [Li].[Fe].P(O)(O)(O)=O Chemical compound [Li].[Fe].P(O)(O)(O)=O ZSYNKHJUSDFTCQ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002999 depolarising effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- HIBWGGKDGCBPTA-UHFFFAOYSA-N C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 HIBWGGKDGCBPTA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 240000003936 Plumbago auriculata Species 0.000 description 1
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002969 artificial stone Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/5825—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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of LiFePO4 doping ternary positive electrode active materials, lithium ion battery and preparation method thereof, it is related to technical field of lithium ion, the LiFePO4 adulterates ternary positive electrode active material, including 30~50 mass parts of 532 type ternary material, 50~65 mass parts and LiFePO4, which has the advantages that energy density is high, discharge capacity is big and voltage range is wide.The LiFePO4 doping ternary positive electrode active material can be widely applied to the preparation of lithium ion battery.
Description
Technical field
The present invention relates to field of lithium ion battery, and tertiary cathode activity material is adulterated in particular to a kind of LiFePO4
Material, lithium ion battery and preparation method thereof.
Background technology
A kind of novel Green Chemistry power supply of lithium ion battery system, has compared with traditional nickel-cadmium cell, Ni-MH battery
The advantage that voltage is high, long lifespan and energy density are big.With the continuous renewal and development of lithium battery technology, light, Gao Rong, length
The advantages of service life, gradually obtains the favor of consumer.Lithium battery market expands to camera, DVD, boat film, toy etc. via mobile phone
Multiple fields.In recent years, lithium ion battery due to have many advantages, such as voltage is high, recycle often, storage time it is long, not only
It is used widely on a portable electronic device, and is widely used in electric vehicle, electric bicycle and electronic work
In terms of the large and medium-sized electrical equipment such as tool.
Existing lithium ion battery includes mainly ternary platform and LiFePO4 platform, however existing ternary battery discharge model
Enclose 4.2~2.75V, ferric phosphate lithium cell platform voltage is 3.65~2.0V, and cell discharge voltage range is relatively narrow, discharge capacity compared with
It is low, it cannot be satisfied and require high field to apply voltage range and discharge capacity.
In view of this, special propose the present invention.
Invention content
The first object of the present invention is to provide a kind of LiFePO4 doping ternary positive electrode active material, the positive-active material
Material has the advantages that energy density is high, discharge capacity is big and voltage range is wide.
The second object of the present invention is to provide a kind of lithium ion battery, which includes that above-mentioned LiFePO4 is mixed
Miscellaneous ternary positive electrode active material, therefore have the advantages that energy density is high, discharge capacity is big and voltage range is wide.
The third object of the present invention is to provide a kind of preparation method of lithium ion battery, and this method is simple for process, science
Rationally, the lithium ion battery being prepared has the advantages that energy density is high, discharge capacity is big and voltage range is wide.
In order to realize that the above-mentioned purpose of the present invention, spy use following technical scheme：
A kind of LiFePO4 provided by the invention adulterates ternary positive electrode active material, including 532 type ternary materials 50~65
30~50 mass parts of mass parts and LiFePO4；
The 532 type ternary material, chemical formula LiNi0.5Mn0.3Co0.2O2。
Further, the LiFePO4 adulterates ternary positive electrode active material, including 532 type ternary material, 55~60 mass
Part and 35~45 mass parts of LiFePO4.
Further, the LiFePO4 adulterates ternary positive electrode active material, including 532 type ternary material, 57~58 matter
Measure part and 38~39 mass parts of LiFePO4；
Preferably, including 532 type ternary material, 57.48 mass parts and 38.32 mass parts of LiFePO4.
Further, the 532 type ternary material is LMO+NCM532 complex ternary materials.
A kind of lithium ion battery provided by the invention, including positive electrode, the positive electrode include above-mentioned ferric phosphate
Lithium doping ternary positive electrode active material.
Further, the positive electrode further includes positive conductive agent and positive electrode binder, positive electrode active materials, just
The mass ratio of pole conductive agent and positive electrode binder is 95~97：1~3：1~3；Preferably 95~96：1~2：1~2；
Preferably, positive conductive agent includes conductive carbon black；
Preferably, positive electrode binder includes PVDF.
Further, the lithium ion battery further includes negative material, and the negative material includes negative electrode active material, bears
The mass ratio of pole conductive agent and negative electrode binder, the negative electrode active material, cathode conductive agent and negative electrode binder is 94~96：
0.5~2：1~4, preferably 94~95：0.5~1：1~2.
Further, the negative electrode active material includes at least one in natural graphite, artificial graphite, soft carbon or hard carbon
Kind.
Further, the cathode conductive agent includes conductive carbon black；
Preferably, negative electrode binder includes thickener and binder；
It is highly preferred that the thickener is CMC, the binder is that the mass ratio of SBR, the CMC and SBR are 0.8：1.
A kind of preparation method of lithium ion battery provided by the invention, includes the following steps：(a) it will include respectively the phosphorus
The positive electrode and negative material of sour iron lithium doping ternary positive electrode active material are coated on plus plate current-collecting body and negative current collector
Then both sides are dried and are compacted, form positive plate and negative plate；
(b) positive plate and negative plate are assembled into battery core by required size；
(c) battery core is subjected to plastic-aluminum membrane envelope, electrolyte is then injected into coating, then sealed up to the lithium-ion electric
Pond.
Compared with prior art, beneficial effects of the present invention are：
LiFePO4 doping ternary positive electrode active material provided by the invention includes 532 type ternary materials and LiFePO4,
532 type ternary materials are adulterated using LiFePO4, effectively compensate for existing ternary battery discharge 4.2~2.75V of range, ferric phosphate
Lithium battery platform voltage is 3.65~2.0V, and cell discharge voltage range is relatively narrow, and discharge capacity is relatively low, cannot be satisfied to voltage model
The problem of requiring high field to be applied with discharge capacity is enclosed, the energy density and electric discharge for improving positive electrode active materials are held
Amount, while reducing cost, be more suitable for commercially producing and applying.
Lithium ion battery provided by the invention includes positive electrode, which includes above-mentioned LiFePO4 doping ternary
Positive electrode active materials, therefore have the advantages that energy density is high, discharge capacity is big and voltage range is wide.
The preparation method of above-mentioned lithium ion battery provided by the invention is simple for process, scientific and reasonable, the lithium being prepared from
Sub- battery has the advantages that energy density is high, discharge capacity is big and voltage range is wide.
Specific implementation mode
Technical scheme of the present invention is clearly and completely described below in conjunction with embodiment, it is clear that described reality
It is a part of the embodiment of the present invention to apply example, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
The every other embodiment that art personnel are obtained without making creative work belongs to the model that the present invention protects
It encloses.
According to an aspect of the present invention, a kind of LiFePO4 adulterates ternary positive electrode active material, including 532 type ternary materials
Expect 50~65 mass parts and 30~50 mass parts of LiFePO4；
The 532 type ternary material, chemical formula LiNi0.5Mn0.3Co0.2O2。
LiFePO4 doping ternary positive electrode active material provided by the invention includes 532 type ternary materials and LiFePO4,
532 type ternary materials are adulterated using LiFePO4, effectively compensate for existing ternary battery discharge 4.2~2.75V of range, ferric phosphate
Lithium battery platform voltage is 3.65~2.0V, and cell discharge voltage range is relatively narrow, and discharge capacity is relatively low, cannot be satisfied to voltage model
The problem of requiring high field to be applied with discharge capacity is enclosed, the energy density and electric discharge for improving positive electrode active materials are held
Amount, while reducing cost, be more suitable for commercially producing and applying.
In NCM ternary materials, the influence of three kinds of nickel (Ni), cobalt (Co), manganese (Mn) elements to material is different, in general,
Ni constituent contents are higher, and the gram volume of material is higher, but then the cycle performance of material and thermal stability will for Ni too high levels
Decline；Co constituent contents are higher, and entire positive electrode active materials system conductivity is higher, and the layer structure of material is better, but Co
Too high levels will increase the manufacturing cost of ternary material, while the thermal stability of material can also decline；Mn contents are higher, material
Cycle performance it is better, thermal stability is higher, but Mn elements are excessively high, and material capacity will be caused to reduce, and is eventually converted into not
The Mn3+ of stability influences the cycle performance of material.
Consider case above, present invention defines the ratios of above-mentioned Ni, Co, Mn, have especially selected 532 type ternary materials
Material, the material each element give full play to respective effect in the positive active material of mono-crystalline structures obtained, and it is living to improve anode
Property material stability, make positive electrode active materials that there is preferable cycle performance, so that final obtained lithium ion battery
With excellent chemical property.
In the preferred embodiment of the present invention, the LiFePO4 adulterates ternary positive electrode active material, including 532
35~45 mass parts of 55~60 mass parts of type ternary material and LiFePO4.
In above-mentioned preferred embodiment, the LiFePO4 adulterates ternary positive electrode active material, including 532 type ternary materials
Expect 57~58 mass parts and 38~39 mass parts of LiFePO4；
Preferably, including 532 type ternary material, 57.48 mass parts and 38.32 mass parts of LiFePO4.
In the present invention, when the mass fraction of above-mentioned 532 type ternary material and LiFePO4 is in above-mentioned preferred range, just
The performance of pole active material is more excellent, and the balance between each performance is more preferable, it is thus possible to make the comprehensive of lithium ion battery
Can be more excellent, practical application effect is more preferable.
In the preferred embodiment of the present invention, the 532 type ternary material is LMO+NCM532 complex ternary materials
Material.
In the present invention, above-mentioned LiFePO4 doping ternary positive electrode active material is mainly by 532 type ternary materials and phosphoric acid
Iron lithium mixes in proportion, hybrid mode use any one existing hybrid mode, the present invention to this not
It is particularly limited.In addition, 532 type ternary materials and LiFePO4 are voluntarily prepared using existing preparation method, this
Invention is not particularly limited this.
According to an aspect of the present invention, a kind of lithium ion battery, including positive electrode, the positive electrode include above-mentioned
LiFePO4 adulterate ternary positive electrode active material.Therefore, above-mentioned lithium ion battery have that energy density is high, discharge capacity is big and
The wide advantage of voltage range.
In the preferred embodiment of the present invention, the positive electrode further includes positive conductive agent, positive electrode binder,
The positive electrode active materials, positive conductive agent, positive electrode binder mass ratio be 95~97：1~3：1~3, preferably 95~
96：1~2：1~2.The mass ratio of positive electrode active materials, positive conductive agent and positive electrode binder is 95~96：1~2：When 1~2,
The viscosity and mobility of positive electrode are more preferable, and the content of LiFePO4 doping ternary positive electrode active material is moderate, is prepared
Lithium ion battery bulk density and security performance higher.
Preferably, positive conductive agent includes conductive carbon black.Conductive carbon black (or conductive black) can improve positive electrode with
Electron-transport between plus plate current-collecting body reduces the interface contact resistance of electrode, plays the role of depolarising.
Preferably, positive electrode binder includes PVDF.PVDF (Polyvinylidene Fluoride) is polyvinyladine floride,
It is a kind of binder of function admirable, cheap, adhesive property is good, helps to improve battery performance.
In the preferred embodiment of the present invention, the lithium ion battery further includes negative material, the cathode material
Material includes negative electrode active material, cathode conductive agent and negative electrode binder, and the negative electrode active material, cathode conductive agent and cathode are viscous
The mass ratio for tying agent is 94~96：0.5~2：1~4, preferably 94~95：0.5~1：1~2.Negative electrode active material, cathode are led
The mass ratio of electric agent and negative electrode binder is 94~96：0.5~2：When 1~4, the viscosity and mobility of negative material are more preferable, and
The content of negative electrode active material is moderate, the energy density higher for the lithium ion battery being prepared.
In above-mentioned preferred embodiment, negative electrode active material includes in natural graphite, artificial graphite, soft carbon or hard carbon
It is at least one.Typical but non-limiting above-mentioned negative electrode active material is natural graphite, artificial graphite, soft carbon, hard carbon, natural stone
The combination of ink and artificial graphite, the combination of soft carbon and hard carbon, the combination of natural graphite, artificial graphite and soft carbon, or, artificial stone
The combination etc. of ink, soft carbon and hard carbon.
Natural graphite cathode active material is using natural flakey Scaly graphite through crushing, nodularization, classification, passivation, table
The processes such as face handle to obtain, what high-crystallinity was naturally occurring.Natural graphite gram volume is higher, simple for process, cheap.
Artificial plumbago negative pole active material is to forge easy graphited carbon (such as petroleum coke, needle coke, pitch coke) at a certain temperature
It burns, then is made through crushing, classification, high temperature graphitization, high-crystallinity is formed by high temperature graphitization.Artificial graphite price
It is higher, but cycle and security performance are preferable.Soft carbon is after heat treatment temperature reaches graphitization temperature, and material has higher graphite
Change degree is easy graphited carbon；It common are coke, graphitized intermediate-phase carbon microballon (MCMB), carbon fiber etc..Soft carbon cathode
Active material has a low and stable charge and discharge potential platform, and charge/discharge capacity is big and efficient, good cycle.Hard carbon refers to
It is difficult to the carbon being graphitized, the crosslinked resin with special construction is thermally decomposed at 1000 DEG C or so can obtain hard carbon, and this kind of carbon exists
2500 DEG C or more of high temperature is also difficult to be graphitized, and common hard carbon has resin carbon and carbon black etc..Hard carbon cathode active material has
There are very high reversible specific capacity, generally 500-700mAh；Hard carbon stable structure and charge and discharge circulation life is long, and carbon lithium current potential
0.2V can be higher than, security performance is more preferable.
In above-mentioned preferred embodiment, cathode conductive agent includes conductive carbon black.Conductive carbon black (or conductive black) can
The electron-transport between positive electrode and plus plate current-collecting body is improved, the interface contact resistance of electrode is reduced, plays the work of depolarising
With.
Preferably, negative electrode binder includes thickener and binder；
It is highly preferred that the thickener is CMC, the binder is SBR.CMC(Sodium
Carboxymethlycellulose) it is sodium carboxymethylcellulose, appearance is white or yellowish fibrous powder or white powder
End, it is odorless, it is tasteless, it is nontoxic；It is soluble in cold water or hot water, forms glue, solution is neutral or alkalescence, in slurry manufacturing process
In can play thickening power.SBR (Styrene Butadiene Rubber) is a kind of styrene-butadiene latex, and aqueous binders are
Emulsifier initiator etc. is added as medium using water by styrene (Styrene) and butadiene (Butadiene) monomer and passes through lotion
Polymerization copolymerization generates, and state is the aqueous emulsion of solid content 50% or so, and cementation, source are mainly played in slurry manufacturing process
Extensively, at low cost.
Preferably, the mass ratio of CMC and SBR is 0.8：1.
According to an aspect of the present invention, a kind of preparation method of above-mentioned lithium ion battery, includes the following steps：(a) divide
The positive electrode that ternary positive electrode active material is adulterated comprising the LiFePO4 and negative material plus plate current-collecting body is not coated on
It with the both sides of negative current collector, is then dried and is compacted, form positive plate and negative plate；
(b) positive plate and negative plate are assembled into battery core by required size；
(c) battery core is subjected to plastic-aluminum membrane envelope, electrolyte is then injected into coating, then sealed up to the lithium-ion electric
Pond.
The preparation method of above-mentioned lithium ion battery is simple for process, scientific and reasonable, and the lithium ion battery being prepared has energy
The advantage that metric density is high, discharge capacity is big and voltage range is wide.
The present invention is not particularly limited the assembling mode of battery core, is assembled using conventional battery core packaging technology
, takeup type battery core or lamination type electric core are such as assembled into using conventional winding or laminating method.
Unmentioned preparation process and parameter in the present invention, such as drying temperature, drying time, compaction pressure, diaphragm and electricity
Selection of liquid etc. is solved according to the conventional selection of this field, the present invention is to this and is not particularly limited.
Technical scheme of the present invention is described further below in conjunction with embodiment and comparative example.
Embodiment 1
A kind of LiFePO4 doping ternary positive electrode active material, including 532 type ternary material, 65 mass parts and LiFePO4
50 mass parts.
Embodiment 2
A kind of LiFePO4 doping ternary positive electrode active material, including 532 type ternary material, 50 mass parts and LiFePO4
30 mass parts.
Embodiment 3
A kind of LiFePO4 doping ternary positive electrode active material, including 532 type ternary material, 60 mass parts and LiFePO4
45 mass parts.
Embodiment 4
A kind of LiFePO4 doping ternary positive electrode active material, including 532 type ternary material, 55 mass parts and LiFePO4
35 mass parts.
Embodiment 5
A kind of LiFePO4 doping ternary positive electrode active material, including 532 type ternary material, 57.48 mass parts and ferric phosphate
38.32 mass parts of lithium.
Embodiment 6
A kind of LiFePO4 doping ternary positive electrode active material, including 532 type ternary material, 57.48 mass parts and ferric phosphate
38.32 mass parts of lithium；
The 532 type ternary material is LMO+NCM532 complex ternary materials.
Embodiment 7~12
A kind of lithium ion battery, including positive electrode and negative material, the positive electrode respectively include Examples 1 to 6
The LiFePO4 adulterates ternary positive electrode active material, further includes positive conductive agent and positive electrode binder, the positive-active
The mass ratio of material, positive conductive agent and positive electrode binder is 90:1:2, positive conductive agent is conductive carbon black, and positive electrode binder is
PVDF；
The negative material includes negative electrode active material, cathode conductive agent and negative electrode binder, the negative electrode active material,
The mass ratio of cathode conductive agent and negative electrode binder is 90:3:1, negative electrode active material is artificial graphite, and cathode conductive agent is to lead
The CMC and SBR for the quality such as electrical carbon is black, and negative electrode binder is.
The preparation method of the lithium ion battery of embodiment 7~12 includes the following steps：(a) it will include respectively the ferric phosphate
The positive electrode and negative material of lithium doping ternary positive electrode active material are coated on the both sides of plus plate current-collecting body and negative current collector,
Then it is dried and is compacted, form positive plate and negative plate；
(b) positive plate and negative plate are assembled into battery core by required size；
(c) battery core is packed into shell, electrolyte is then injected into shell, then sealed up to the lithium ion battery.
Effect example 1
To show the lithium ion battery of the invention being prepared, have energy density height, discharge capacity big and voltage range
Wide advantage.It is existing special by embodiment 11, the lithium ion battery that embodiment 12 is prepared and common ferric phosphate lithium cell into
Row performance detection, testing result are as shown in table 1.
Table 1：The performance test results of lithium ion battery
In conclusion LiFePO4 doping ternary positive electrode active material of the present invention includes 532 type ternary materials and ferric phosphate
Lithium adulterates 532 type ternary materials using LiFePO4, effectively compensates for existing ternary battery discharge 4.2~2.75V of range, phosphorus
Sour lithium iron battery platform voltage is 3.65~2.0V, and cell discharge voltage range is relatively narrow, and discharge capacity is relatively low, cannot be satisfied to electricity
The problem of pressure range and discharge capacity require high field to be applied.As seen from the above table, have the lithium that is prepared of the present invention from
Sub- battery voltage range can reach 4.2~2.0V, and battery capacity, constant current ratio and energy density are obviously higher than common phosphoric acid
Lithium iron battery, and then the present invention improves the energy density and discharge capacity of positive electrode active materials, while cost is reduced, more
It is suitble to commercially produce and applies.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of LiFePO4 adulterates ternary positive electrode active material, which is characterized in that including 532 type ternary material, 50~65 mass
Part and 30~50 mass parts of LiFePO4；
The 532 type ternary material, chemical formula LiNi0.5Mn0.3Co0.2O2。
2. LiFePO4 according to claim 1 adulterates ternary positive electrode active material, which is characterized in that including 532 types three
35~45 mass parts of 55~60 mass parts of first material and LiFePO4.
3. LiFePO4 according to claim 1 adulterates ternary positive electrode active material, which is characterized in that including 532 types three
38~39 mass parts of 57~58 mass parts of first material and LiFePO4；
Preferably, including 532 type ternary material, 57.48 mass parts and 38.32 mass parts of LiFePO4.
4. adulterating ternary positive electrode active material according to claims 1 to 3 any one of them LiFePO4, which is characterized in that institute
It is LMO+NCM532 complex ternary materials to state 532 type ternary materials.
5. a kind of lithium ion battery, which is characterized in that including positive electrode, the positive electrode includes that Claims 1 to 4 is any
LiFePO4 described in adulterates ternary positive electrode active material.
6. lithium ion battery according to claim 5, which is characterized in that the positive electrode further include positive conductive agent and
The mass ratio of positive electrode binder, the positive electrode active materials, positive conductive agent and positive electrode binder is 95~97：1~3：1~3；
Preferably 95~96：1~2：1~2；
Preferably, positive conductive agent includes conductive carbon black；
Preferably, positive electrode binder includes PVDF.
7. lithium ion battery according to claim 5 or 6, which is characterized in that the lithium ion battery further includes cathode material
Material, the negative material includes negative electrode active material, cathode conductive agent and negative electrode binder, the negative electrode active material, cathode
The mass ratio of conductive agent and negative electrode binder is 94~96：0.5~2：1~4, preferably 94~95：0.5~1：1~2.
8. lithium ion battery according to claim 7, which is characterized in that the negative electrode active material include natural graphite,
At least one of artificial graphite, soft carbon or hard carbon.
9. lithium ion battery according to claim 7, which is characterized in that the cathode conductive agent includes conductive carbon black；
Preferably, negative electrode binder includes thickener and binder；
It is highly preferred that the thickener is CMC, the binder is that the mass ratio of SBR, the CMC and SBR are 0.8：1.
10. a kind of preparation method according to claim 5~9 any one of them lithium ion battery, which is characterized in that including with
Lower step：(a) positive electrode that ternary positive electrode active material is adulterated comprising the LiFePO4 and negative material are coated respectively
It in the both sides of plus plate current-collecting body and negative current collector, is then dried and is compacted, form positive plate and negative plate；
(b) positive plate and negative plate are assembled into battery core by required size；
(c) battery core is subjected to plastic-aluminum membrane envelope, electrolyte is then injected into coating, then sealed up to the lithium ion battery.
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