CN107565135A - Application, lithium ion cell electrode, its preparation method and application of a kind of fluorophosphates in lithium ion cell electrode is prepared - Google Patents
Application, lithium ion cell electrode, its preparation method and application of a kind of fluorophosphates in lithium ion cell electrode is prepared Download PDFInfo
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- CN107565135A CN107565135A CN201610528803.3A CN201610528803A CN107565135A CN 107565135 A CN107565135 A CN 107565135A CN 201610528803 A CN201610528803 A CN 201610528803A CN 107565135 A CN107565135 A CN 107565135A
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides application, lithium ion cell electrode, its preparation method and application of a kind of fluorophosphates in lithium ion cell electrode is prepared, the lithium ion cell electrode includes collector and is supported on electrode material thereon, the electrode material is made up of the slurry including additive, and the additive is the fluorophosphates shown in Formulas I；Wherein, M is alkali metal, and 0 ＜ a≤3, x and y is integer, 1≤x, y≤4, x+y≤5.The present invention prepares lithium ion cell electrode using the fluorophosphates shown in Formulas I, can effectively improve the polarization situation of pole piece, improves SEI membrane stabilities, improves pole piece analysis lithium situation.Lithium ion cell electrode manufacturing cost provided by the invention is low, and after being assembled into battery, battery high rate performance significantly improves, and lithium situation is obviously improved, cyclical stability is also obviously improved for analysis, and battery safety is improved.MaPOxFyFormulas I.
Description
Technical field
The present invention relates to technical field of lithium ion secondary, more particularly to a kind of fluorophosphates to prepare lithium-ion electric
Application, lithium ion cell electrode, its preparation method and application in the electrode of pond.
Background technology
Lithium ion battery is because with operating voltage is high, energy density is big, self-discharge rate is low, memory-less effect, cycle life
The advantages that long and pollution-free, it is widely used in the every field of daily life, including various portable electric appts and electronic vapour
Car etc..But with the fast development of science and technology, portable electric appts are miniaturized, grow standby, the long-life development, and electronic
Automobile etc. is high-power, it is high-energy device enable, energy density, circulation all to the lithium rechargeable battery as accumulation power supply
The performances such as life-span, adaptive capacity to environment propose higher and higher requirement.
In the battery design of reality, by being adulterated to positive and negative pole material, coating modification, or function is added in the electrolytic solution
The modes such as property additive improve the performances such as the cycle life of battery, and these are the main stream approach in current industry.Pass through raising
The weight/mass percentage composition of active material or the thickness for increasing pole piece, and one of effective ways of lifting battery energy density.So
And there is following defect in existing method：1. in cyclic process first, electrolyte and electrode material in lithium-ion battery system
It can be reacted between solid liquid phase in aspect, one layer of SEI film of formation, the process will consume the lithium in electrode material activity material,
So as to cause lithium ion battery initial capacity relatively low；2. in charge and discharge process, certain thickness pole piece cause battery formed compared with
Big concentration polarization, so cause battery capacity not play normally, high rate performance is poor, low temperature analysis lithium, Capacity fading etc.
A series of problems.
In order to improve above mentioned problem, in existing technology, the Chinese patent literature of Application No. 201210415398.6
By the way that lithium source is coated in polymer after formation nucleocapsid clad structure, it is added in electrode material, to improve battery because first
Capacitance loss caused by discharge and recharge film forming.The lithium that can be made up caused by forming SEI films using the method is lost, but its
This is higher for actual industrial chemical conversion, meanwhile, this method also is difficult to ensure that lithium simple substance can be coated and in high temperature pole piece technique completely
In can be stabilized, be unfavorable for the application in lithium ion battery.
The content of the invention
In view of this, the application provides a kind of application in lithium ion cell electrode is prepared of fluorophosphates, lithium ion
Battery electrode, its preparation method and application, using lithium ion cell electrode provided by the invention, high rate performance and safety can be obtained
The battery of the excellent performances such as performance, and cost is low.
The present invention provides application of the fluorophosphates in lithium ion cell electrode is prepared, and the fluorophosphates have formula
I formulas：
MaPOxFyFormulas I；
Wherein, M is alkali metal, and 0 ＜ a≤3, x and y is integer, 1≤x, y≤4, x+y≤5.
The present invention provides a kind of lithium ion cell electrode, including collector and the electrode material that is supported on the collector
Material；The electrode material is made up of the slurry including additive, and the additive is the fluorophosphates shown in Formulas I；
MaPOxFyFormulas I；
Wherein, M is alkali metal, and 0 ＜ a≤3, x and y is integer, 1≤x, y≤4, x+y≤5.
Preferably, the M is selected from Li, Na, K or Rb, y≤3, x+y≤4.
Preferably, the weight/mass percentage composition that the fluorophosphates account in lithium ion battery electrode material be 0.1~
15%.
Preferably, the lithium ion battery electrode material is by including fluorophosphates, active material, conductive agent and binding agent
Slurry be made；In terms of mass fraction, the slurry includes：0.1~15% fluorophosphates, 55~99% active matter
Matter, 0.1~15% conductive agent and 0.1~15% binding agent.
Preferably, the lithium ion cell electrode is positive pole, and active material is selected from transition metal oxide in the positive pole
Or transient metal sulfide.
Preferably, the lithium ion cell electrode is negative pole, and active material is selected from containing lithium metal, lithium titanate in the negative pole
Material, carbon material, transition metal oxide material or silicon materials.
The present invention provides a kind of preparation method of lithium ion cell electrode, comprises the following steps：
By the slurry coating including additive on a current collector, simultaneously roll-in is dried, obtains lithium ion cell electrode；It is described to add
Add agent for the fluorophosphates shown in Formulas I；
MaPOxFyFormulas I；
Wherein, M is alkali metal, and 0 ＜ a≤3, x and y is integer, 1≤x, y≤4, x+y≤5.
Preferably, the temperature of the drying is 80~200 DEG C.
The present invention also provides a kind of lithium ion battery, and it includes electrode described above.
Compared with prior art, the present invention prepares lithium ion cell electrode using the fluorophosphates shown in Formulas I, can be effective
Improve the polarization situation of pole piece, improve SEI membrane stabilities, improve pole piece analysis lithium situation.Lithium-ion electric provided by the invention
Pond electrode manufacturing cost is low, and after battery is made, battery high rate performance is significantly improved, and cycle life is obviously prolonged, battery security
It can be improved.
Brief description of the drawings
Fig. 1 is that fluorophosphates add the contrast schematic diagram in pole piece and electrolyte.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
The invention provides application of the fluorophosphates in lithium ion cell electrode is prepared, the fluorophosphates have
Formulas I formula：
MaPOxFyFormulas I；
Wherein, M is alkali metal, and 0 ＜ a≤3, x and y is integer, 1≤x, y≤4, x+y≤5.
The present invention is using the fluorophosphates shown in Formulas I as lithium ion cell electrode additive, for preparing lithium-ion electric
Pond electrode, the conductive capability of pole piece can be effectively improved, and can improve pole piece polarization, analysis lithium in pole piece film forming
With the stability of SEI films, it can fully improve the performance of battery, additionally it is possible to reduce cost, be allowed to be suitably applied lithium ion two
Primary cell.
In the present invention, the fluorophosphates have Formulas I formula.Wherein, M is alkali metal, preferably lithium (Li),
Sodium (Na), potassium (K) or rubidium (Rb), more preferably Li or Na.In Formulas I, 0 ＜ a≤3, preferably 1 or 2.X and y is integer, 1≤
X, y≤4, x+y≤5.Preferably, 1≤x, y≤3, x+y≤4.In a preferred embodiment of the invention, x=y=2.Specifically
, the fluorophosphates can be LiPO2F2、NaPO2F2、KPO2F2And Li2PO3F etc..In the present invention, the fluoro shown in Formulas I
Phosphate can be commercially available prod, can also be by being prepared.
In the present invention, the weight/mass percentage composition that the fluorophosphates account in lithium ion battery electrode material is preferably
0.1~15%, more preferably 0.1~10%, more preferably 0.2~8%, most preferably 1~6%.In the reality of the present invention
Apply in example, in the structure such as Fig. 1 of the electrode plates containing the fluorophosphates shown in (b), Fig. 1 is that fluorophosphates add
Contrast schematic diagram in pole piece and electrolyte.In Fig. 1, (a) is that fluorophosphates add in the electrolytic solution, and (b) is fluorophosphate
Salt is added in pole piece；1 is the SEI films that fluorophosphates are main component, and 2 be active material, and 3 be fluorophosphates, and 4 be collection
Fluid.As shown in Figure 1, in electrode plates of the present invention containing the fluorophosphates, fluorophosphates can be coated on active matter
On matter particle, significantly improve electrode performance.
The invention provides a kind of lithium ion cell electrode, including collector and the electrode material that is supported on the collector
Material；The electrode material is made up of the slurry including additive, and the additive is the fluorophosphates shown in Formulas I；
MaPOxFyFormulas I；
Wherein, M is alkali metal, and 0 ＜ a≤3, x and y is integer, 1≤x, y≤4, x+y≤5.
Using lithium ion cell electrode provided by the invention, the electricity of the excellent performances such as high rate performance and security performance can be obtained
Pond, and cost is reduced, suitable for industrial application.
The embodiment of the present invention uses the fluorophosphates shown in Formulas I that lithium ion is made for lithium ion cell electrode additive
Battery electrode.Wherein, the fluorophosphates have Formulas I formula, and M is alkali metal, preferably lithium (Li), sodium (Na), potassium
Or rubidium (Rb), more preferably Li or Na (K).In Formulas I, 0 ＜ a≤3, preferably 1 or 2.X and y is integer, 1≤x, y≤4, x+
y≤5.Preferably, 1≤x, y≤3, x+y≤4.In a preferred embodiment of the invention, x=y=2.Specifically, the fluoro
Phosphate can be LiPO2F2、NaPO2F2、KPO2F2And Li2PO3F etc..In the present invention, the fluorophosphates shown in Formulas I can be
Commercially available prod, can also be by being prepared.
In the present invention, the weight/mass percentage composition that the fluorophosphates account in lithium ion battery electrode material is preferably
0.1~15%, more preferably 0.1~10%, more preferably 0.2~8%, most preferably 1~6%.The present invention can lead to
The addition of fluorophosphates in the electrodes is overregulated, obtains the more excellent battery of performance.In an embodiment of the present invention, contain
There is structure such as (b) in Fig. 1 of the electrode plates of the fluorophosphates shown.
In an embodiment of the present invention, the lithium ion battery electrode material by including fluorophosphates, active material, lead
The slurry of electric agent and binding agent is made.The lithium ion cell electrode is pole piece, can be positive plate, or negative plate.
The lithium ion cell electrode can be positive pole, and active material (or active material, active component) can be this in the positive pole
Usually used any transition metal oxide or transient metal sulfide in field.For example, cobalt acid lithium (LiCoO2)、
LiMntO2t(t=1 or 2), LiNi1-tMntO2(0≤t ＜ 1), LiNitCo1-tO2(0 ＜ t ＜ 1), nickel manganese cobalt acid lithium (LiNi1/ 3Mn1/3Co1/3O2、Li1.2Ni1/6Mn1/6Co4/6O2), LiFePO4 (LiFePO4) etc. the various transition metal combined oxidations containing lithium
Thing, and for example MoS2、SnS2、MoO3、V2O5Etc. various transition metal oxides or transient metal sulfide without lithium, preferably contain
The compound transition metal oxide of lithium.The above positive electrode active materials can be obtained commercially, can also pass through system
It is standby to obtain.
In the present invention, the lithium ion cell electrode can also be negative pole, and active material can be existing in the negative pole
There are any negative electrode active material commercially available from energy in technology, including lithium metal or lithium alloy；The titanium with dedoping lithium ion can be adulterated
Sour lithium material；The carbon material with dedoping lithium ion can be adulterated；The transition metal oxide material with dedoping lithium ion can be adulterated
Material such as tin oxide, niobium oxide, vanadium oxide, titanium oxide；Or silicon materials with dedoping lithium ion can be adulterated.Present invention preferably employs
The carbon material with dedoping lithium ion can be adulterated, such carbon material can be graphite, or amorphous carbon, such as activity
Charcoal, carbon fiber, carbon black, native graphite etc..
Anode sizing agent in the embodiment of the present invention can be by the fluorophosphates, positive electrode active materials, conductive agent, adhesive
Formed Deng mixing, cathode size can be then made up of mixing such as the fluorophosphates, negative active core-shell material, conductive agent, adhesives.
Wherein, carbon black, acetylene black may be used as conductive agent (or conductive material).Adhesive (or binding agent) can be selected from inclined difluoro second
Alkene/hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene (PTFE) and its
Mixture or the polymer based on butadiene-styrene rubber (SBR).In the present invention, the group such as the conductive agent in positive pole and negative pole, binding agent
Dividing can be with identical, can also be different.
In an embodiment of the present invention, the fluorophosphates, active material, conductive agent and binding agent etc. can according to lithium from
Usually used dosage composition slurry in sub- battery.In terms of mass fraction, the slurry preferably includes：0.1~15% fluoro
Phosphate, 55~99% active material, 0.1~15% conductive agent and 0.1~15% binding agent.Wherein, the fluoro
Phosphatic weight/mass percentage composition is more preferably 0.1~10%, more preferably 0.2~8%, most preferably 1~6%.Institute
The weight/mass percentage composition for stating active material is more preferably 60~97%, most preferably 75~95%.The quality hundred of the conductive agent
Point content is more preferably 0.5~10%, most preferably 1~8%.The weight/mass percentage composition of the binding agent is more preferably 0.5~
10%, most preferably 1~7%.
The lithium ion cell electrode includes collector, and the present invention is not particularly limited to it, using commonly used in the art
, such as copper foil, aluminium foil.
Correspondingly, the invention provides a kind of preparation method of lithium ion cell electrode, comprise the following steps：
By the slurry coating including additive on a current collector, simultaneously roll-in is dried, obtains lithium ion cell electrode；It is described to add
Add agent for the fluorophosphates shown in Formulas I；
MaPOxFyFormulas I；
Wherein, M is alkali metal, and 0 ＜ a≤3, x and y is integer, 1≤x, y≤4, x+y≤5.
The embodiment of the present invention provides the slurry including additive first, and the additive is the fluorophosphates shown in Formulas I,
Its content is as it was noted above, this is no longer going to repeat them.In an embodiment of the present invention, the slurry includes active material, led
Electric agent and binding agent, the contents of these components is also as mentioned before.The slurry also includes solvent, such as organic solvent or water, uses
To disperse or dissolve said components.The solvent is preferably 1-METHYLPYRROLIDONE (NMP), acetone or water, and the present invention is used it
Amount is not particularly limited.
In an embodiment of the present invention, the quality of fluorophosphates in the slurry, active material, conductive agent and binding agent
Proportioning is preferably：Fluorophosphates 0.1~15%, active material 55~99%, conductive agent 0.1~15%, binding agent 0.1~
15%；Slurry solid content is 10~90%.And more preferably：Fluorophosphates 0.1~10%, active material 60~
97%th, conductive agent 0.5~10%, binding agent 0.5~10%；Slurry solid content is 30~85%.More preferably：Fluorophosphates
0.2~8%, active material 75~95%, conductive agent 1~8%, binding agent 1~7%；Slurry solid content is 40~70%.
The present invention is not particularly limited to the preparation method of the slurry, for example during making positive pole, can be added in a solvent
Fluorophosphates, stirring and dissolving, it is configured to phosphate solution containing fluoro；Then by positive active material, conductive agent and binding agent
Add in above-mentioned solution, be stirred into uniform slurry.The solid masses content (i.e. solid content) of the slurry is preferably 10
~90%, more preferably 30~85%, most preferably 40~70%.
After obtaining slurry, the embodiment of the present invention is dried it was evenly coated on collector, then through roll-in, cut, obtain
To lithium ion cell electrode.The lithium ion cell electrode includes collector, and the present invention is not particularly limited to it, using ability
Domain is conventional.
In the present invention, the lithium ion cell electrode includes the electrode material of load on a current collector, the electrode material
Material by slurry it is coated, drying be made.The drying can be by the way of drying, and temperature is preferably 80~200 DEG C, more preferably
For 100~150 DEG C, above-mentioned fluorophosphates can be made to keep stable.The time of the drying can be 1 minute~50 minutes；It is described
Roll-in is technological means well known to those skilled in the art, and the present invention is not particularly limited.
Lithium ion cell positive can be prepared in the present invention, and negative pole can also be prepared.Lithium-ion electric in the present invention
Preparation is simple for pond electrode, and manufacturing cost is low, is suitably applied lithium rechargeable battery.By the lithium ion of the present invention
After battery is made in battery electrode, battery high rate performance is significantly improved, and cycle life is obviously prolonged, and battery safety is carried
It is high.
Present invention also offers a kind of lithium ion battery, and it includes electrode described above, has excellent high rate performance
And security performance, and cost is low.
In an embodiment of the present invention, the structure of the lithium ion battery can be wrapped using the conventional structure in this area
Include housing, electrolyte, barrier film, positive plate and negative plate.Wherein, the positive plate and/or negative plate can be described above
Electrode, it will not be repeated here.
In an embodiment of the present invention, the barrier film can in well known to a person skilled in the art lithium ion battery institute
Various membrane layers, for example, it is polyolefin micro porous polyolefin membrane (PP micro-porous films), polyethylene felt (PE felts), glass mat, ultra-fine
All-glass paper or PP/PE/PP composite membranes.As a preferred embodiment, the barrier film is PP/PE/PP composite membranes.
In an embodiment of the present invention, the electrolyte is nonaqueous electrolytic solution, contains lithium salts and nonaqueous solvents.Wherein, institute
It can be lithium hexafluoro phosphate (LiPF to state lithium salts6), LiBF4, hexafluoroarsenate lithium, lithium perchlorate, trifluoromethyl sulfonic acid lithium,
One in perfluoro butyl Sulfonic Lithium, lithium aluminate, chlorine lithium aluminate, fluoro sulfimide lithium, fluorophosphate lithium, lithium chloride and lithium iodide
Kind or several, preferably LiPF6.The nonaqueous solvents can be gamma-butyrolacton, methyl ethyl carbonate (EMC), methyl propyl carbonate,
Dipropyl carbonate, acid anhydrides, 1-METHYLPYRROLIDONE, N-METHYLFORMAMIDE, N- methylacetamides, acetonitrile, N, N- dimethyl formyls
In amine, sulfolane, dimethyl sulfoxide, dimethyl sulfite and other fluorine-containing, sulfur-bearings or ring-type organic ester containing unsaturated bond
One or more in one or more, preferably ethylene carbonate (EC), diethyl carbonate (DEC) and EMC.The present invention's
In preferred embodiment, the nonaqueous solvents is EC/EMC/DEC mixed solvent, and the volume ratio of three can be 1:1:1.The lithium
The concentration of salt in the electrolytic solution can be 0.3~4 mol/L, preferably 0.5~2 mol/L.
The present invention can prepare lithium ion battery, in general, the party according to method known in those skilled in the art
Method includes：Positive pole, negative pole and the barrier film between positive pole and negative pole are wound successively, pole piece is formed, the pole piece is inserted
In battery container, electrolyte is added, is then sealed, be melted into, lithium ion battery is made.Wherein, the positive pole include collector and
The positive electrode of load on a current collector, the negative pole include the negative material of collector and load on a current collector；In both
At least one is electrode described above, and another can be this area conventional electrodes.The housing is using commonly used in the art
, such as battery aluminum shell.The winding, sealing and the method for chemical conversion are the technological means well known to those skilled in the art；It is described
The dosage of electrolyte is also conventional amount used.
The lithium ion battery of the present invention can be cylindrical shape, Coin shape, square and other arbitrary shapes；The shape of battery with
Basic structure is unrelated, can implement design alteration according to purpose.The present invention carries out performance test to the lithium ion battery, including
Normal-temperature circulating performance test, 45 DEG C of cycle performance tests, the test of 5C high rate performances.As a result show, it is provided by the invention to contain fluorine
After being assembled into battery for phosphatic pole piece, battery has preferable normal-temperature circulating performance, and high temperature circulation has good stability, multiplying power
Performance also has more obvious raising.In addition, lithium ion cell electrode manufacturing cost provided by the invention is low, beneficial to actual industrial
Change and promote.
For a further understanding of the application, with reference to embodiment to the fluorophosphates that the application provides prepare lithium from
Application, lithium ion cell electrode, its preparation method and application in sub- battery electrode are specifically described.
In following examples, fluorophosphates used are purchased from Jing Hua new materials Co., Ltd of Shenzhen.
Embodiment 1
1st, the making of positive pole：The two of total positive pole mass fraction of solids 3% is added in 1-METHYLPYRROLIDONE (NMP) solvent
Sodium fluoro phosphate stirring and dissolving, using the 88% cobalt acid lithium (LiCoO as positive active material2), 4% as conductive material
Acetylene black, 5% adhesive Kynoar (PVDF) are added in solution, and uniform sizing material is made in stirring, and slurry solid content is
55%, it is 12 μm of aluminium foil two sides that obtained slurry is coated on into thickness, and in 120 DEG C of dryings, then through roll-in, cut, obtain
Positive pole.
2nd, the making of negative pole：By the Delanium (China fir Taxodiaceae skill, SS1-P10) of total negative pole mass fraction of solids 95%, 2%
Binding agent butadiene-styrene rubber it is newborn (SBR), 1% binding agent carboxymethyl cellulose (CMC), 2% conductive material SP and water add
Mixed to disperser, slurry is made, slurry solid content is 35%.Obtained slurry is coated on the copper foil that thickness is 10 μm
Two sides, and dry, then through roll-in, cut, obtain negative pole.
3rd, the assembling of secondary cell：Above-mentioned positive pole, negative pole and polypropylene screen (PP/PE/PP) are wound into a side respectively
The pole piece of type lithium ion battery, then by LiPF6Mixed solvent (EC is dissolved in by the concentration of 1 mol/L：EMC：DEC=1:1:
1 volume ratio) in, nonaqueous electrolytic solution is formed, the electrolyte is injected in battery aluminum shell with 3.7g/Ah amount, sealing, 0.1C normal temperature
Chemical conversion, is made lithium ion battery.
Embodiment 2
Positive pole, negative pole and battery are prepared using method and steps same as Example 1, the difference is that in positive electrode
Fluorophosphates are difluorophosphate.
Embodiment 3
Positive pole, negative pole and battery are prepared using method and steps same as Example 1, the difference is that in positive electrode
Fluorophosphates are difluorophosphate, and positive electrode active materials are LiFePO4, and each component ratio is difluorophosphate 5%, phosphoric acid
Iron lithium 89%, acetylene black 3%, binding agent Kynoar 3%, slurry solid content are 60%.
Embodiment 4
Positive pole, negative pole and battery are prepared using method and steps same as Example 1, the difference is that in positive electrode
Fluorophosphates are difluorophosphate, and positive electrode active materials are nickel manganese cobalt acid lithium (LiNi1/3Mn1/3Co1/3O2)。
Embodiment 5
Positive pole, negative pole and battery are prepared using method and steps same as Example 1, the difference is that in positive electrode
Fluorophosphates are difluorophosphoric acid potassium, and positive electrode active materials are nickel manganese cobalt acid lithium (Li1.2Ni1/6Mn1/6Co4/6O2)。
Embodiment 6
Positive pole, negative pole and battery are prepared using method and steps same as Example 1, the difference is that in positive electrode
Fluorophosphates are difluorophosphate, and positive electrode active materials are nickel manganese cobalt acid lithium (LiNi1/3Mn1/3Co1/3O2), each component ratio
For difluorophosphate 1%, nickel manganese cobalt acid lithium 90%, acetylene black 5%, binding agent Kynoar 4%, slurry solid content is
58%.
Embodiment 7
1st, the making of positive pole：Total positive pole mass fraction of solids 92% is added in 1-METHYLPYRROLIDONE (NMP) solvent
Cobalt acid lithium (LiCoO as positive active material2), 3% as the acetylene black of conductive material, 5% adhesive gather inclined fluorine
Ethene (PVDF) is added in solution, and uniform sizing material is made in stirring, and slurry solid content is 55%, and obtained slurry is coated on into thickness
For 12 μm of aluminium foil two sides, and in 120 DEG C of dryings, then through roll-in, cut, obtain positive pole.
2nd, the making of negative pole：The difluorophosphoric acid sodium stirring for adding total negative pole mass fraction of solids 3% in deionized water is molten
Solution, then newborn (SBR), the 1% binding agent carboxymethyl cellulose by 92% Delanium, 2% binding agent butadiene-styrene rubber
(CMC), 2% conductive material SP adds disperser and mixed, and slurry is made, and slurry solid content is 35%.The slurry that will be obtained
It is 10 μm of copper foil two sides that material, which is coated on thickness, and is dried, then through roll-in, cut, obtain negative pole.
3rd, the assembling of secondary cell：Above-mentioned positive pole, negative pole and polypropylene screen are wound into a square lithium-ion electricity respectively
The pole piece in pond, then by LiPF6Mixed solvent (EC is dissolved in by the concentration of 1 mol/L：EMC：DEC=1:1:1 volume ratio)
In, nonaqueous electrolytic solution is formed, the electrolyte is injected in battery aluminum shell with 3.7g/Ah amount, seals, chemical conversion, lithium ion is made
Battery.
Embodiment 8
Positive pole, negative pole and battery are prepared using method and steps same as Example 7, the difference is that in negative material
Fluorophosphates are difluorophosphate.
Embodiment 9
Positive pole, negative pole and battery are prepared using method and steps same as Example 1, the difference is that in negative material
Fluorophosphates are difluorophosphate, and negative active core-shell material is native graphite (China fir Taxodiaceae skill, DMGS), and each component ratio is difluoro
Lithium phosphate 5%, native graphite 89%, SP 3%, SBR 2%, CMC 1%, slurry solid content are 45%.
Embodiment 10
Positive pole, negative pole and battery are prepared using method and steps same as Example 7, the difference is that in negative material
Fluorophosphates are difluorophosphate, and negative active core-shell material is silicon-carbon cathode (China fir Taxodiaceae skill, Si-C-S-3).
Embodiment 11
Positive pole, negative pole and battery are prepared using method and steps same as Example 7, the difference is that in negative material
Fluorophosphates are difluorophosphoric acid potassium, each component ratio be difluorophosphoric acid potassium 2%, Delanium 92%, SP 3%, SBR 2%,
CMC 1%, slurry solid content are 45%.
Embodiment 12
1st, the making of positive pole：The two of total positive pole mass fraction of solids 3% is added in 1-METHYLPYRROLIDONE (NMP) solvent
Lithium fluophosphate stirring and dissolving, using the 88% cobalt acid lithium (LiCoO as positive active material2), 4% as conductive material
Acetylene black, 5% adhesive Kynoar (PVDF) add stirring in solution and uniform sizing material are made, and slurry solid content is
55%, it is 12 μm of aluminium foil two sides that obtained slurry is coated on into thickness, and in 120 DEG C of dryings, then through roll-in, cut, obtain
Positive pole.
2nd, the making of negative pole：The difluorophosphate stirring for adding total negative pole mass fraction of solids 3% in deionized water is molten
Solution, then newborn (SBR), the 1% binding agent carboxymethyl cellulose by 92% Delanium, 2% binding agent butadiene-styrene rubber
(CMC), 2% conductive material SP is added and mixed in disperser, and slurry is made, and slurry solid content is 35%.By what is obtained
It is 10 μm of copper foil two sides that slurry, which is coated on thickness, and is dried, then through roll-in, cut, obtain negative pole.
3rd, the assembling of secondary cell：Above-mentioned positive pole, negative pole and polypropylene screen are wound into a square lithium-ion electricity respectively
The pole piece in pond, then by LiPF6Mixed solvent (EC is dissolved in by the concentration of 1 mol/L：EMC：DEC=1:1:1) in, formed
Nonaqueous electrolytic solution, the electrolyte is injected in battery aluminum shell with 3.7g/Ah amount, seals, chemical conversion, lithium ion battery is made.
Embodiment 13
Positive pole, negative pole and battery are prepared using method and steps same as Example 7, the difference is that in negative material
Fluorophosphates are Li2PO3F, each component ratio are Li2PO3F 2%, Delanium 92%, SP 3%, SBR 2%, CMC
1%, slurry solid content is 45%.
Embodiment 14
Positive pole, negative pole and battery are prepared using method and steps same as Example 1, the difference is that in negative material
Fluorophosphates are difluorophosphate, and negative active core-shell material is native graphite (China fir Taxodiaceae skill, DMGS), and each component ratio is difluoro
Lithium phosphate 15%, native graphite 79%, SP 3%, SBR 2%, CMC 1%, slurry solid content are 45%.
Embodiment 15
Positive pole, negative pole and battery are prepared using method and steps same as Example 1, the difference is that in negative material
Fluorophosphates are difluorophosphate, and negative active core-shell material is native graphite (China fir Taxodiaceae skill, DMGS), and each component ratio is difluoro
Lithium phosphate 0.2%, native graphite 93.8%, SP 3%, SBR 2%, CMC 1%, slurry solid content are 45%.
Embodiment 16
Positive pole, negative pole and battery are prepared using method and steps same as Example 1, the difference is that drying temperature is
180℃。
Comparative example 1
1st, the making of positive pole：Total positive pole mass fraction of solids 92% is added in 1-METHYLPYRROLIDONE (NMP) solvent
Cobalt acid lithium (LiCoO as positive active material2), 3% as the acetylene black of conductive material, 5% adhesive gather inclined fluorine
Ethene (PVDF) is added in solution, and uniform sizing material is made in stirring, and slurry solid content is 55%, and obtained slurry is coated on into thickness
For 12 μm of aluminium foil two sides, and in 120 DEG C of dryings, then through roll-in, cut, obtain positive pole.
2nd, the making of negative pole：By the Delanium of total negative pole mass fraction of solids 95%, 2% binding agent butadiene-styrene rubber breast
(SBR), 1% binding agent carboxymethyl cellulose (CMC), 2% conductive material SP and water are added to disperser and mixed, system
Into slurry, slurry solid content is 35%.Obtained slurry is coated on the copper foil two sides that thickness is 10 μm, and dried, then through roller
Press, cut, obtain negative pole.
3rd, the assembling of secondary cell：Above-mentioned positive pole, negative pole and polypropylene screen are wound into a square lithium-ion electricity respectively
The pole piece in pond, then by LiPF6Mixed solvent (EC is dissolved in by the concentration of 1 mol/L：EMC：DEC=1:1:1 volume ratio)
In, nonaqueous electrolytic solution is formed, the electrolyte is injected in battery aluminum shell with 3.7g/Ah amount, seals, chemical conversion, lithium ion is made
Battery.
The battery performance test of embodiment 12
1st, the normal-temperature circulating performance test of battery
The resultant battery that will be obtained in embodiment 1~16 and comparative example 1, is tested in such a way respectively：In room
Under temperature, 0.05C is first dropped to 1C electric current constant-current charge to 4.2V, then constant-voltage charge to electric current, it is finally permanent with 1C electric current
Stream is discharged to 3.0V.So circulation 300 weeks, the record discharge capacity and the discharge capacity of the 500th week of the 1st week, then basis with
Lower formula, the capability retention of the normal temperature circulation of battery is calculated, result of calculation is shown in table 1 below, and table 1 is embodiment and comparative example
The performance test results of middle lithium ion battery；
Discharge capacity × 100% of the discharge capacity of capability retention=300th week/1st week.
2nd, 45 DEG C of cycle performances test of battery
The resultant battery that will be obtained in embodiment 1~16 and comparative example 1, is tested in such a way respectively：45
Under the conditions of DEG C, 0.05C is first dropped to 1C electric current constant-current charge to 4.2V, then constant-voltage charge to electric current, then with 1C electricity
Constant-current discharge is flowed to 3.0V.So circulation 300 weeks, the record discharge capacity and the discharge capacity of the 300th week of the 1st week, Ran Hougen
According to below equation：The capability retention of 45 DEG C of circulations of battery is calculated, result of calculation is shown in table 1 below；
Discharge capacity × 100% of the discharge capacity of capability retention=300th week/1st week.
3rd, the 5C high rate performances test of battery
The resultant battery that will be obtained in embodiment 1~16 and comparative example 1, is tested in such a way respectively：Normal
Under the conditions of temperature, 0.05C is first dropped to 1C electric current constant-current charge to 4.2V, then constant-voltage charge to electric current, then with 5C electricity
Constant-current discharge is flowed to 3.0V.So circulation 50 weeks, record the 1C discharge capacities and the 5C discharge capacities of the 50th week of the 1st week, then
According to below equation, the capability retention of the normal temperature multiplying power of battery is calculated, result of calculation is shown in table 1 below；
1C discharge capacity × 100% of the discharge capacity of capability retention=50th week/1st week.
The performance test results of lithium ion battery in the embodiment of table 1 and comparative example
From the data of table 1：After pole piece provided by the invention containing fluorophosphates is assembled into battery, battery have compared with
Good normal-temperature circulating performance, high temperature circulation have good stability, and high rate performance also has more obvious raising, illustrates fluorophosphates
Addition, improve the stability of inside battery polarization and SEI films, simultaneously because the excellent electrical conductivity of fluorophosphates, improve
The internal resistance of cell.
Described above is only the preferred embodiment of the present invention, it is noted that the professional technique for making the art
Personnel, without departing from the technical principles of the invention, it is that by a variety of modifications to these embodiments, and these
Modification also should be regarded as the scope that the present invention should protect.
Claims (10)
1. application of the fluorophosphates in lithium ion cell electrode is prepared, the fluorophosphates have Formulas I formula：
MaPOxFyFormulas I；
Wherein, M is alkali metal, and 0 ＜ a≤3, x and y is integer, 1≤x, y≤4, x+y≤5.
2. a kind of lithium ion cell electrode, including collector and the electrode material that is supported on the collector；The electrode material
Material is made up of the slurry including additive, and the additive is the fluorophosphates shown in Formulas I；
MaPOxFyFormulas I；
Wherein, M is alkali metal, and 0 ＜ a≤3, x and y is integer, 1≤x, y≤4, x+y≤5.
3. lithium ion cell electrode according to claim 2, it is characterised in that the M is selected from Li, Na, K or Rb, y≤3,
x+y≤4。
4. lithium ion cell electrode according to claim 2, it is characterised in that the fluorophosphates are in lithium ion battery
The weight/mass percentage composition accounted in electrode material is 0.1~15%.
5. lithium ion cell electrode according to claim 2, it is characterised in that the lithium ion battery electrode material is by wrapping
The slurry for including fluorophosphates, active material, conductive agent and binding agent is made；In terms of mass fraction, the slurry includes：0.1
~15% fluorophosphates, 55~99% active material, 0.1~15% conductive agent and 0.1~15% binding agent.
6. lithium ion cell electrode according to claim 5, it is characterised in that the lithium ion cell electrode is positive pole,
Active material is selected from transition metal oxide or transient metal sulfide in the positive pole.
7. lithium ion cell electrode according to claim 5, it is characterised in that the lithium ion cell electrode is negative pole,
Active material, which is selected from, in the negative pole contains lithium metal, lithium titanate material, carbon material, transition metal oxide material or silicon materials.
8. a kind of preparation method of lithium ion cell electrode, comprises the following steps：
By the slurry coating including additive on a current collector, simultaneously roll-in is dried, obtains lithium ion cell electrode；The additive
For the fluorophosphates shown in Formulas I；
MaPOxFyFormulas I；
Wherein, M is alkali metal, and 0 ＜ a≤3, x and y is integer, 1≤x, y≤4, x+y≤5.
9. preparation method according to claim 8, it is characterised in that the temperature of the drying is 80~200 DEG C.
10. a kind of lithium ion battery, it is characterised in that including the electrode or claim 8 described in any one of claim 2~7
Electrode made from preparation method described in~9 any one.
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| CN201610528803.3A CN107565135A (en) | 2016-06-30 | 2016-06-30 | Application, lithium ion cell electrode, its preparation method and application of a kind of fluorophosphates in lithium ion cell electrode is prepared |
| PCT/CN2017/090557 WO2018001274A1 (en) | 2016-06-30 | 2017-06-28 | Application of fluorophosphate in preparation of lithium ion battery electrode, lithium ion battery electrode and preparation method therefor and application thereof |
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