CN105098138A - Negative plate used for lithium ion battery and preparation method thereof - Google Patents
Negative plate used for lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention provides an integrative negative plate used for a lithium ion battery. The integrative negative plate is prepared from negative electrode materials and metal powder, wherein the metal powder does not form alloy with metal lithium. The invention also provides a preparation method of the integrative negative plate and the lithium ion battery which contains the above integrative negative plate. The integrative negative plate has good comprehensive performance and excellent negative plate conductivity, and the specific energy density of the unit volume or the unit mass of the battery is greater than the specific energy density of a common lithium ion battery.
Description
Technical field
The present invention relates to a kind of negative electrode for lithium ion battery sheet and preparation method thereof.
Background technology
The negative material of lithium ion battery mainly contains material with carbon element, silicon materials, nitrogen lithium compound (lithium transition-metal nitride), metal oxide, intermetallic compound and conductive organic polymer.Current commercial use more be graphitized carbon material.This type of material conductivity is good, and degree of crystallinity is higher, has good layer structure, is applicable to the embedding-deintercalation of lithium, forms lithium-compound between graphite layers.But this type of material charging and discharging capacity is not high, generally between 300 ~ 400mAh/g.The non-carbon negative material finding height ratio capacity is the focus of current lithium ion battery material research.Wherein elemental silicon is the material of most practical prospect.Silicon and lithium generate Li
4.4si, its theoretical discharge specific capacity can reach 4200mAh/g.But, in charge and discharge process the Infix and desfix of lithium ion cause material volume tempestuously Swelling and contraction (during charging, Lithium-ion embeding causes silicon materials volumetric expansion, can more than 300% be reached), silicon material structure is caused to destroy and efflorescence, cause the disengaging between material, between material and conductive agent and between material and collector, electron conduction reduces, and finally causes the capacity of battery sharply to reduce.In addition, also there is the problems such as the less and conductivity of lithium ion diffusion coefficient is not high in silicon materials.
Many researchers once proposed various solution, and its main thought silicon is made nano particle or is prepared into porous silicon, as nano silicon crystal, nano cilicon fibre, nano carbon tube, mesoporous or porous nano silicon etc.Porous nano silicon materials have the advantages such as short, the mechanical plasticity of lithium ion the evolving path is strong, electrolyte solution wetability is good, effectively can improve capacity and the invertibity of the embedding lithium of silicon materials-Tuo lithium, and improve the mechanical strength of material to a certain extent, the change in volume that the Infix and desfix due to lithium ion causes can be tolerated, delay the advantage such as to collapse of material structure.But the electronic conductance performance of silicon is not good, and nano-porous structure can not improve the conductivity of silicon materials; In addition, porous nano silicon materials have larger specific area, and material surface and electrolyte react and forms passivation layer (SEI film), though this layer can transmit electronics and lithium ion, but more active lithium can be consumed, cause the irreversible loss (first charge-discharge efficiency is low) of initial capacity.Silicon alloy and Si-C composite material are the practical developing direction of silica-base material.The inert metal that do not react with Li is introduced or material with carbon element can promote ionic conductivity and the structural stability of silicon materials effectively as conductive agent and support structure skeleton in silicon materials, and reduce the contact area of silicon and electrolyte solution, reduce the loss of active lithium, improve first charge-discharge efficiency to a certain extent.The researchers such as Xu Caixia prepare nanoporous silicon alloy (Chinese patent CN201310092226.4) and nanoporous Si-C composite material (Chinese patent CN201310092227.9) by the method for strong acid or the polynary silicon-containing alloy of alkali corrosion.As compared to the preparation technology such as template, chemical vapour deposition technique, electrochemical oxidation process, electroless plating method and the coated carbonizatin method of organic polymer, the technique being prepared silicon alloy and Si-C composite material by multicomponent alloy has simple to operate and that cost is low advantage.But etch also inevitably exists some problems, as repeatedly produced a large amount of waste water with water cleaning material, stoichiometric side product chlorinated aluminium, aluminum sulfate or the sodium aluminates such as generation; And produce hydrogen when corroding, need during large-scale production to deal carefully with the dangerous H of tool
2.Moreover, still there is the problem that first charge-discharge efficiency is low in the silicon alloy that silicon and 3d metal form and Si-C composite material.During charging, Lithium-ion embeding silicon forms silicon lithium alloy, and during electric discharge, lithium ion can not realize complete deintercalation.Therefore, how improving first charge-discharge efficiency is a great problem that silicon based anode material commercialization faces.
Current, the cathode pole piece of lithium ion battery is generally evenly coated on Copper Foil both sides by active material and conductive agent, adhesive, solvent after being mixed and made into slurry by a certain percentage, then drying and roll extrusion are made.This traditional pole piece processing method operation is longer, need to consume solvent or dispersant, and the adhesive used in the manufacturing process of present lithium ion battery is nonconducting organic high molecular polymer, as fluorine resin, polyolefin compound, butadiene-styrene rubber or carboxymethyl cellulose etc., introduce the content that adhesive not only reduces active material in pole piece, reduce battery capacity, and reduce the electronic conductance ability of pole piece, affect the performance of battery.When water-insoluble organic polymers such as selecting fluorine resin, polyolefin compound, butadiene-styrene rubber makes adhesive, also need to select organic solvent, there is solvent and chemical reaction may occur active material, and recycle the problem of solvent.Therefore, in conjunction with the characteristic of silica-base material, find new pole piece manufacture method, avoid the drawback existed in conventional method, be also impel silicon based anode material realize early business-like in the urgent need to.
Summary of the invention
The invention provides a kind of negative electrode for lithium ion battery sheet and preparation method thereof.Negative electrode for lithium ion battery sheet of the present invention is a kind of negative plate of integration.
One object of the present invention is to provide a kind of Integral load pole piece for lithium ion battery, and the raw material of this Integral load pole piece comprises negative material and metal powder, and this Integral load pole piece is suppressed by described raw material and formed.
In the present invention, described metal powder is the powder of the metal except lithium.The metal powder (or particle) being not easy to be formed with lithium alloy selected by metal powder, and wherein the particle diameter of metal powder is less than 100 microns.Above-mentioned metal powder can as filler and/or covering.
In the present invention, the described metal powder (or particle) being not easy to be formed with lithium metal alloy refers to the powder of lithium metal those metals that solubility is little in this metal.Above-mentioned metal powder can be selected from the powder (or particle) that Ni metal, Ag, Au, Ni, Co, Fe, Mn, Zn and the alloy containing Cu, Ag, Au, Ni, Co, Fe, Mn or Zn are formed, but is not restricted to this several metal material.
According to one embodiment of the present invention, above-mentioned metal powder is selected from the powder (or particle) that Ni metal, Ag, Au, Zn and the alloy containing Cu, Ag, Au or Zn are formed.Preferably, above-mentioned metal powder is selected from the powder (or particle) of Cu, Zn and the formation of their alloy.
According to one embodiment of the present invention, the powder (or particle) that above-mentioned metal powder is selected from Cu and is formed containing the alloy of Cu.
In the present invention in order to realize object of the present invention, negative material selects particle diameter to be less than the negative material of 20 microns.
In the present invention, the preferred jumbo negative material of described negative material, such as capacity is at the negative material of more than 400mAh/g.
According to one embodiment of the present invention, above-mentioned negative material is selected from Si(silicon), Li-Si alloy, Fe
3o
4, B(boron), Sn, SnO, black phosphorus, NiO, TiO
2and at least one in their mixture.
According to one embodiment of the present invention, above-mentioned negative material is Si(silicon).
According to one embodiment of the present invention, above-mentioned negative material is Li-Si alloy.
According to one embodiment of the present invention, above-mentioned negative material is B(boron).
According to one embodiment of the present invention, above-mentioned negative material is Sn.
According to one embodiment of the present invention, above-mentioned negative material is Fe
3o
4.
According to one embodiment of the present invention, above-mentioned negative material is SnO.
According to one embodiment of the present invention, above-mentioned negative material is NiO.
According to one embodiment of the present invention, above-mentioned negative material is TiO
2.
The preferred jumbo negative material of negative material in the present invention, such as capacity is greater than the negative material of 400mAh/g.Because use metal powder (or particle) to do the clad material of negative material in the present invention, metal powder (or particle) can take segment space volume and weight, if adopt the negative material of low capacity as graphite or lithium titanate negative plate, the capacity of final obtained negative plate can be lower, is difficult to the demand meeting cell integrated energy density.Therefore, the present invention preferably uses Si(silicon), Li-Si alloy, Fe
3o
4, B(boron), Sn, SnO, black phosphorus, NiO, TiO
2and the material such as their mixture does negative material, but the present invention is not restricted to this different materials or their composite materials of being mixed into by a certain percentage.
According to one embodiment of the present invention, the raw material of above-mentioned Integral load pole piece comprises negative material, metal powder and lithium powder, and this Integral load pole piece is suppressed by described raw material and formed.
In order to fully improve the capacity of battery, lithium powder is made an addition in the material making negative plate, lithium powder can as benefit lithium material.The particle diameter of above-mentioned lithium powder is preferably less than 200 microns.In the present invention, above-mentioned benefit lithium is a kind of selection, and can not mend lithium in some negative plate, the present invention can select whether mend lithium according to actual needs.When needs carry out benefit lithium, be preferably less than the lithium powder benefit lithium of 200 microns with particle diameter, mend lithium amount and determine according to actual needs.
According to another embodiment of the invention, the raw material of above-mentioned Integral load pole piece comprises negative material, metal powder, lithium powder and leads lithium ion additive, and this Integral load pole piece is suppressed by described raw material and formed.
In the present invention, in order to construct more lithium ion tunnel in negative plate, by add lead that lithium ion additive improves negative plate lead lithium ion ability.Described lithium ion additive of leading can be selected from conductive carbon black, carbon nano-tube, Graphene, Li
4ti
5o
12, LiBO
2, Li
3pO
4, Li
nsi(n is 0.1 ~ 4), Li
2s, Li
mb(m is 0.1 ~ 3) and Li
3at least one in N etc., but be not restricted to these materials.
According to another embodiment of the invention, the raw material of above-mentioned Integral load pole piece comprises negative material, metal powder, lithium powder, leads lithium ion additive and structure enhancing support material, and this Integral load pole piece is suppressed by described raw material and formed.
In the present invention, it is the material that can strengthen negative plate intensity that above-mentioned structure strengthens support material, porous chips, film, the cloth be made into and net that general the selection of material is made, above-mentioned structure strengthen support material when suppressing negative plate and other material there is good combination.Such as structure enhancing support material can be selected from least one in carbon cloth or carbon fibre web, high molecular polymer cloth or high molecular polymer net, porous metals sheet, porous alloy sheet, foam metal, foamed alloy, wire netting and alloy network etc., and described metal is the metal being not easy to be formed with lithium alloy.Use these materials can strengthen the intensity of negative plate.
According to one embodiment of the present invention, said structure strengthens support material and is selected from aramid fabric or aramid fiber net.
According to one embodiment of the present invention, said structure enhancing support material is selected from least one in porous metals sheet and porous alloy sheet, and described metal is selected from Cu, Ag, Au and Zn, and described alloy is selected from the alloy containing Ni metal, Ag, Au or Zn.
According to one embodiment of the present invention, said structure enhancing support material is selected from least one in foam metal and foamed alloy, and described metal is selected from Cu, Ni and Zn, and described alloy is selected from the alloy containing Ni metal, Ni or Zn.
Do according to one embodiment of the present invention, said structure strengthens support material and is selected from foamed alloy, and described alloy is selected from the alloy containing Ni metal.
Do according to one embodiment of the present invention, said structure enhancing support material is selected from least one in wire netting and alloy network, and described metal is selected from Cu, Ni, Ag, Au and Zn, and described alloy is selected from the alloy containing Ni metal, Ni, Ag, Au or Zn.
Do according to one embodiment of the present invention, said structure strengthens support material and is selected from alloy network, and described alloy is the alloy containing Ni metal.
Another object of the present invention is the preparation method providing a kind of Integral load pole piece for lithium ion battery, comprises the steps: 1) a kind of raw material of Integral load pole piece is provided, described raw material comprises negative material and a kind of metal powder; 2) described raw material mixing compacting is formed Integral load pole piece.
In the present invention, negative material selects particle diameter to be less than the negative material of 20 microns.The preferred jumbo negative material of described negative material, such as capacity is at the negative material of more than 400mAh/g.
According to one embodiment of the present invention, above-mentioned negative material is selected from Si(silicon), Li-Si alloy, Fe
3o
4, B(boron), Sn, SnO, black phosphorus, NiO, TiO
2and at least one in their mixture.
In the present invention, the metal powder (or particle) being not easy to be formed with lithium metal alloy selected by metal powder, and wherein the particle diameter of metal powder is less than 100 microns.Above-mentioned metal powder can as filler and/or covering.
In the present invention, the described metal powder (or particle) being not easy to be formed with lithium metal alloy refers to the powder of lithium metal those metals that solubility is little in this metal.Above-mentioned metal powder can be selected from the powder (or particle) that Ni metal, Ag, Au, Ni, Co, Fe, Mn, Zn and the alloy containing Cu, Ag, Au, Ni, Co, Fe, Mn or Zn are formed, but is not restricted to this several metal material.
According to one embodiment of the present invention, above-mentioned metal powder is selected from the powder (or particle) that Ni metal, Ag, Au, Zn and the alloy containing Cu, Ag, Au or Zn are formed.Preferably, above-mentioned metal powder is selected from the powder (or particle) of Cu, Zn and the formation of their alloy.
According to one embodiment of the present invention, the powder (or particle) that above-mentioned metal powder is selected from Cu and is formed containing the alloy of Cu.
According to one embodiment of the present invention, the invention provides a kind of preparation method of the Integral load pole piece for lithium ion battery, comprise the steps: 1) a kind of raw material of Integral load pole piece is provided, described raw material comprises negative material, a kind of metal powder and lithium powder; 2) described raw material mixing compacting is formed Integral load pole piece.
The particle diameter of above-mentioned lithium powder is preferably less than 200 microns.In the present invention, above-mentioned benefit lithium is a kind of selection, and can not mend lithium in some negative plate, the present invention can select whether mend lithium according to actual needs.When needs carry out benefit lithium, be preferably less than the lithium powder benefit lithium of 200 microns with particle diameter, mend lithium amount and determine according to actual needs.
According to one embodiment of the present invention, the invention provides a kind of preparation method of the Integral load pole piece for lithium ion battery, comprise the steps: 1) a kind of raw material of Integral load pole piece is provided, described raw material comprises negative material, a kind of metal powder, lithium powder and one and leads lithium ion additive; 2) described raw material mixing compacting is formed Integral load pole piece.
In the present invention, by add lead that lithium ion additive improves negative plate lead lithium ion ability.Described lithium ion additive of leading can be selected from conductive carbon black, carbon nano-tube, Graphene, Li
4ti
5o
12, LiBO
2, Li
3pO
4, Li
nsi(n is 0.1 ~ 4), Li
2s, Li
nb(n is 0.1 ~ 3), Li
3at least one in N etc., but be not restricted to these materials.
According to one embodiment of the present invention, the invention provides a kind of preparation method of the Integral load pole piece for lithium ion battery, comprise the steps: 1) provide that a kind of raw material of Integral load pole piece, described raw material comprise negative material, a kind of metal powder, lithium powder, one leads lithium ion additive and a kind of structure strengthens support material; 2) described raw material mixing compacting is formed Integral load pole piece.
In the present invention, described structure strengthens porous chips, film, the cloth be made into and the net that the general the selection of material of support material is made, this structure strengthen support material when suppressing negative plate and other material there is good combination.Described structure enhancing support material can be selected from least one in carbon cloth or carbon fibre web, high molecular polymer cloth or high molecular polymer net, porous metals sheet, porous alloy sheet, foam metal, foamed alloy, wire netting and alloy network etc., and described metal is the metal being not easy to be formed with lithium alloy.Use these materials can strengthen the intensity of negative plate.
According to one embodiment of the present invention, said structure strengthens support material and is selected from aramid fabric or aramid fiber net.
According to one embodiment of the present invention, said structure enhancing support material is selected from least one in porous metals sheet and porous alloy sheet, and described metal is selected from Cu, Ag, Au and Zn, and described alloy is selected from the alloy containing Ni metal, Ag, Au or Zn.
According to one embodiment of the present invention, said structure enhancing support material is selected from least one in foam metal and foamed alloy, and described metal is selected from Cu, Ni and Zn, and described alloy is selected from the alloy containing Ni metal, Ni or Zn.
According to one embodiment of the present invention, said structure strengthens support material and is selected from foamed alloy, and described alloy is selected from the alloy containing Ni metal.
According to one embodiment of the present invention, said structure enhancing support material is selected from least one in wire netting and alloy network, and described metal is selected from Cu, Ni, Ag, Au and Zn, and described alloy is selected from the alloy containing Ni metal, Ni, Ag, Au or Zn.
According to one embodiment of the present invention, said structure strengthens support material and is selected from alloy network, and described alloy is the alloy containing Ni metal.
According to one embodiment of the present invention, above-mentioned in steps 2) in, described raw material mixing compacting is formed Integral load pole piece to carry out all in an inert atmosphere.
According to the preparation method of the Integral load pole piece for lithium ion battery of the present invention, above-mentioned steps 2) in compacting be adopt the way of roll-in to carry out obtained lithium ion battery Integral load pole piece.
In the present invention, in order to increase pole piece intensity, usually selecting carbon cloth or carbon fibre web, high molecular polymer cloth or high molecular polymer to arrange net as required, being not easy to be formed with lithium metal the porous metals sheet of alloy or wire netting is that structure strengthens support material.If do not adopt structure to strengthen support material, the material provided in step 1) can be carried out after mixing is pressed into pole piece, then laser scanning is carried out to pole piece and sinter to obtain Integral load pole piece, or using plasma carries out thermal sintering to pole piece and obtains Integral load pole piece.According to one embodiment of the present invention, above-mentionedly laser scanning sintering or using plasma are carried out to pole piece thermal sintering is carried out to pole piece carry out in an inert atmosphere.
According to one embodiment of the present invention, first by negative material, metal powder, lithium powder with lead lithium ion additive and mix, obtain pole piece through roll-in, then laser scanning is carried out to pole piece and sinter to obtain Integral load pole piece.
According to one embodiment of the present invention, first by negative material, metal powder, lithium powder with lead lithium ion additive and mix, obtain pole piece through roll-in, then with plasma, thermal sintering process is carried out to pole piece and obtain Integral load pole piece.
According to another embodiment of the invention, the invention provides a kind of preparation method of the Integral load pole piece for lithium ion battery, comprise the steps: 1) provide a kind of negative material, a kind of metal powder, lithium powder, one to lead lithium ion additive, a kind of structure enhancing support material and a kind of liquid dispersed agent; 2) by described negative material, metal powder, lithium powder, lead lithium ion additive and add in liquid dispersed agent to mix and make slurry; 3) described slurry being coated described structure strengthens in support material, then volatilization removing dispersant, through suppressing to obtain Integral load pole piece.Above-mentioned liquid dispersed agent is the liquid dispersant do not reacted with lithium powder.
In the present invention, described liquid dispersed agent is the organic solvent that can volatilize do not reacted with lithium metal or the organic solution being dissolved with other component, is at room temperature such as hydrocarbon compound and the ether compound of liquid.The effect of dispersant helps each component powder of electrode processed to be mutually mixed and made into mixed uniformly slurry.
According to one embodiment of the present invention, described liquid dispersed agent is selected from toluene, dimethylbenzene, the carbon number alkene between 7 to 20, the alkane of carbon number between 7 to 20 and at least one in aromatic hydrocarbons.
According to one embodiment of the present invention, described liquid dispersed agent is the ether of carbon number between 7 to 20.
According to one embodiment of the present invention, described liquid dispersed agent is that paraffin is dissolved in the solution formed in alkene between 7 to 20 of toluene, dimethylbenzene, carbon number or the alkane of carbon number between 7 to 20, and wherein paraffin mass content is in the solution between 0.1% to 20%.
According to one embodiment of the present invention, described liquid dispersed agent is the solution that paraffin is dissolved in carbon number and is formed in the ether of 7 to 20, and wherein paraffin mass content is in the solution between 0.1% to 20%.
Another object of the present invention is to provide a kind of lithium ion battery, comprise Integral load pole piece as above.
The present invention adopts Large Copacity negative material to mix with metal powder, utilize the ductility of metal, and metal has the character of non-reversible deformation under pressure, can there is irreversible plastic deformation in metal powder (or particle), porous metals sheet and wire netting etc. in nipping process.In deformation process, the space between Large Copacity negative material particle filled under pressure by metal powder as far as possible, realizes the coated of metal pair Large Copacity negative material particle; On the other hand, because metal has elasticity in various degree, after removing the pressure all can part resilience, so small gap can be produced between metal and Large Copacity negative material particle.These gaps can allow the electrolyte solution of trace enter formation lithium ion tunnel on the one hand, and the change in volume that these gaps produce for lithium ion turnover Large Copacity negative material particle on the other hand provides tolerance space, is conducive to the structure of stable cell negative plate.In order to strengthen the intensity of negative plate further, a kind of method carries out sintering processes to pole piece after compacting pole piece, such as does sintering processes with laser or plasma to pole piece or pole piece be heated to the fusing point close to clad metal and carry out roll-in.The another kind of method improving pole piece intensity negative material, metal powder, additive and/or lithium powder is dispersed in structure strengthen in support material, on the porous metals sheet strengthen support material carbon cloth or carbon fibre web, high molecular polymer cloth or high molecular polymer net as being dispersed in structure, being not easy to form alloy with lithium metal or wire netting, then carry out roll-in.Such as in order to realize object of the present invention, select the metal powder (or particle) being not easy to be formed with lithium metal alloy as filler and covering in the present invention, carbon cloth or carbon fiber is selected to arrange net, high molecular polymer cloth or high molecular polymer net, the porous metals sheet or the wire netting that are not easy to be formed with lithium metal alloy are that structure strengthens support material, the Large Copacity negative material selecting particle diameter to be less than 20 microns is negative material, the lithium metal selecting particle diameter to be less than 200 microns is that negative pole is mended lithium active material and selected and can strengthen the material of leading lithium ion ability and do being made into one of additive negative plate.In the manufacturing process of another kind of Integral load pole piece, first metal powder, Large Copacity negative material powder, lithium powder with lead lithium ion additive and add in liquid dispersed agent (liquid dispersed agent is the liquid compound do not reacted with lithium powder) to mix and make slurry, slurry is coated structure to be strengthened in support material, then dispersant is removed in volatilization, obtains pole piece through roll-in.In Integral load pole piece of the present invention, metal component ensure that pole piece good lead electro, the gap between metal and Large Copacity negative material particle can allow electrolyte to enter, ensure that pole piece good lead lithium ion performance; Structure strengthens support material and ensure that the mechanical structure stability that pole piece is good.So integrated battery cathode sheet of the present invention has good combination property, useful life, the specific energy density of battery unit volume or Unit Weight was higher than conventional lithium-ion battery than general battery cathode length of a film.
The present invention adopt directly negative material, rise the coated and supporting function of negative material metal powder, lithium powder, lead lithium ion additive or/and structural reinforcement material is pressed into the method for negative plate, prepared Integral load pole piece compared with prior art has the following advantages: (1) is owing to can regulate the content of lithium in negative plate neatly, when making battery, the positive electrode in corresponding positive plate can not contain lithium ion; (2) when positive electrode is traditional composite oxide of metal containing lithium ion, negative pole can improve battery capacity by supplementing lithium; (3) owing to adopting metal to suppress together with Large Copacity negative material, negative plate has excellent conductivity; (4) owing to plaing a part, negative material is coated also plays collector with metal powder that is supporting function after being pressed, and negative plate can not need special collector; (5) integrated battery cathode sheet of the present invention does not need to use adhesive, improves the conductivity of negative plate.
Accompanying drawing explanation
Fig. 1: button cell the 5th cycle charge-discharge curve in embodiment 1;
Fig. 2: button cell the 5th cycle charge-discharge curve in embodiment 2;
Fig. 3: button cell the 5th cycle charge-discharge curve in embodiment 3;
Fig. 4: button cell second time cycle charge-discharge curve in embodiment 4.
Embodiment
Following specific embodiment is to invention has been detailed description, but the present invention is not restricted to following examples.
In enforcement ion of the present invention, what select in battery preparation is PVDF barrier film, and electrolyte solution is the LiPF of 1.0mol/L
6be dissolved in EMC/EC/DC(1:1:1) in mixed solvent, operation preparation CR2025 button cell in glove box.
embodiment 1:V
2
o
5
positive pole is to Li-Si-Cu integration negative pole
V
2o
5prepared by anode pole piece: blended anode material V
2o
5(0.800g), conductive black (0.100g), PVDF(0.100g) and NMP(2.00g) prepare slurry, coat pole piece processed on aluminium foil (thick 125 μm of pole piece), then dry, the disk that pole piece is cut into 15mm uses, compacting under 2.0MPa after section.
Prepared by cathode pole piece: in glove box under argon atmospher, take the Li of 0.0300g
13si
4it is mould inner pressure sheet (10.0MPa) negative plate processed of 14.0mm that the copper powder of powder, 0.1200g mixes at diameter, then with V
2o
5positive plate assembled battery, battery measurement result is as shown in Fig. 1 and table 1.
Button cell discharge and recharge data in table 1, embodiment 1.
| Cycle-index | Bound voltage (V) | Charging capacity (mAh/g) | Discharge capacity (mAh/g) | Middle pressure (V) |
| 1 | 0.5-3.8 | -- | 349 | 0.905 |
| 2 | 0.5-3.8 | 311 | 231 | 1.586 |
| 3 | 0.5-3.8 | 206 | 323 | 1.846 |
| 4 | 0.5-3.8 | 230 | 191 | 1.982 |
| 5 | 0.5-3.8 | 186 | 184 | 1.998 |
| 6 | 0.5-3.8 | 183 | 180 | 1.983 |
| 7 | 0.5-3.8 | 177 | 177 | 1.968 |
| 8 | 0.5-3.8 | 173 | 171 | 1.933 |
| 9 | 0.5-3.8 | 172 | 169 | 1.888 |
| 10 | 0.5-3.8 | 170 | 168 | 1.815 |
| 11 | 1-3.8 | 164 | 168 | 1.929 |
| 12 | 1-3.8 | 151 | 148 | 1.931 |
| 20 | 1-3.8 | 140 | 143 | 1.940 |
*: this battery charging and discharging capacity presses positive pole V
2o
5mass Calculation.
embodiment 2:V
2
o
5
positive pole is to Li-Si-Cu integration negative pole:
V
2o
5prepared by anode pole piece: blended anode material V
2o
5(0.800g), conductive black (0.100g), PVDF(0.100g) and NMP(2.00g) prepare slurry, coat pole piece processed on aluminium foil (thick 125 μm of pole piece), then dry, the disk that pole piece is cut into 15mm uses, compacting under 2.0MPa after section.
Prepared by cathode pole piece: in glove box under argon atmospher, take the Cu powder of 0.0800g, the lithium powder of 0.0100g, the silica flour of 0.0100g mix and put into the foam copper matrix that diameter is 14mm, at mould inner pressure sheet (10.0MPa) negative plate processed that diameter is 14.0mm, then with V
2o
5positive plate assembled battery, battery measurement result is as shown in Fig. 2 and table 2.
Button cell discharge and recharge data in table 2, embodiment 2.
| Cycle-index | Bound voltage (V) | Charging capacity (mAh/g) | Discharge capacity (mAh/g) | Middle pressure (V) |
| 1 | 0.5-3.8 | -- | 493 | 1.854 |
| 2 | 0.5-3.8 | 287 | 247 | 1.998 |
| 3 | 0.5-3.8 | 281 | 254 | 2.026 |
| 4 | 0.5-3.8 | 237 | 231 | 2.039 |
| 5 | 0.5-3.8 | 226 | 231 | 2.023 |
| 6 | 0.5-3.8 | 231 | 228 | 2.015 |
| 7 | 0.5-3.8 | 224 | 225 | 2.005 |
| 8 | 0.5-3.8 | 223 | 223 | 1.997 |
| 9 | 0.5-3.8 | 217 | 216 | 1.987 |
| 10 | 0.5-3.8 | 210 | 209 | 1.979 |
| 11 | 0.5-3.8 | 203 | 202 | 1.969 |
| 12 | 0.5-3.8 | 198 | 198 | 1.962 |
| 20 | 0.5-3.8 | 156 | 158 | 1.889 |
*: this battery charging and discharging capacity presses positive pole V
2o
5mass Calculation.
embodiment 3:V 2 o 5 positive pole is to Li-Si-Cu integration negative pole:
V
2o
5prepared by anode pole piece: blended anode material V
2o
5(0.800g), conductive black (0.100g), PVDF(0.100g) and NMP(2.00g) prepare slurry, coat pole piece processed on aluminium foil (thick 125 μm of pole piece), then dry, the disk that pole piece is cut into 15mm uses, compacting under 2.0MPa after blade.
Prepared by cathode pole piece: in glove box under argon atmospher, take the Cu powder of 0.0800g and the Li of 0.0200g
13si
4powder mixes puts into the foam copper matrix that diameter is 14mm, is mould inner pressure sheet (10.0MPa) negative plate processed of 14.0mm, then with V at diameter
2o
5positive plate assembled battery, battery measurement result is as shown in Fig. 3 and table 3.
Button cell discharge and recharge data in table 3, embodiment 3.
| Cycle-index | Bound voltage (V) | Charging capacity (mAh/g) | Discharge capacity (mAh/g) | Middle pressure (V) |
| 1 | 0.5-3.8 | -- | 263 | 1.266 |
| 2 | 0.5-3.8 | 332 | 257 | 1.944 |
| 3 | 0.5-3.8 | 274 | 240 | 1.928 |
| 4 | 0.5-3.8 | 222 | 214 | 1.946 |
| 5 | 0.5-3.8 | 221 | 214 | 1.954 |
| 6 | 0.5-3.8 | 220 | 212 | 1.959 |
| 7 | 0.5-3.8 | 217 | 210 | 1.96 |
| 8 | 0.5-3.8 | 214 | 208 | 1.962 |
| 9 | 0.5-3.8 | 214 | 207 | 1.959 |
| 10 | 0.5-3.8 | 212 | 205 | 1.961 |
| 11 | 0.5-3.8 | 211 | 201 | 1.951 |
| 12 | 0.5-3.8 | 212 | 197 | 1.935 |
| 15 | 0.5-3.8 | 210 | 190 | 1.942 |
*: this battery charging and discharging capacity presses positive pole V
2o
5mass Calculation.
embodiment 4:NCM positive pole is to Li-Si-Cu Integral load
The preparation of NCM anode pole piece: mixing LiNiCoMnO
x(NCM5KBDA) positive electrode 0.8000g, conductive black 0.1000g, PVDF0.1000g, NMP(2.000g) be coated with pole piece (thickness 125 μm) after slurrying material, then dry, pole piece is cut into the disk of 15mm, compacting under 2.0MPa, is placed in drying box for subsequent use.
Prepared by cathode pole piece: in glove box under argon atmospher, take the Cu powder of 0.0800g, the lithium powder of 0.0050g, the silica flour of 0.0150g mix at diameter is mould inner pressure sheet (10.0MPa) negative plate processed of 14.0mm, then with the assembled battery of NCM positive plate, battery measurement result is as shown in Fig. 4 and table 4.
Button cell discharge and recharge data in table 4, embodiment 4.
| Cycle-index | Bound voltage (V) | Charging capacity (mAh/g) | Discharge capacity (mAh/g) | Middle pressure (V) |
| 1 | 2.5-4.0 | 178 | 126 | 3.312 |
| 2 | 2.5-4.0 | 174 | 127 | 3.257 |
| 3 | 2.5-4.0 | 148 | 107 | 3.229 |
| 4 | 2.5-4.2 | 119 | 119 | 3.253 |
| 5 | 2.5-4.2 | 125 | 125 | 3.236 |
| 6 | 2.5-4.2 | 125 | 124 | 3.256 |
| 7 | 2.5-4.2 | 129 | 125 | 3.267 |
| 8 | 2.5-4.2 | 127 | 124 | 3.277 |
*: this battery charging and discharging capacity presses the active material Mass Calculation of positive pole NCM.
Claims (36)
1. for an Integral load pole piece for lithium ion battery, the raw material of this Integral load pole piece comprises negative material and metal powder, and this Integral load pole piece is suppressed by described raw material and formed.
2. Integral load pole piece according to claim 1, is characterized in that, described metal powder is selected from the powder that Ni metal, Ag, Au, Ni, Co, Fe, Mn, Zn and the alloy containing Cu, Ag, Au, Ni, Co, Fe, Mn or Zn are formed.
3. Integral load pole piece according to claim 2, is characterized in that, described metal powder is selected from the powder that Ni metal, Ag, Au, Zn and the alloy containing Cu, Ag, Au or Zn are formed.
4. Integral load pole piece according to claim 3, is characterized in that, described metal powder is selected from the powder of Cu, Zn and the formation of their alloy.
5. Integral load pole piece according to claim 3, is characterized in that, the powder that described metal powder is selected from Cu and is formed containing the alloy of Cu.
6., according to the arbitrary described Integral load pole piece of claim 1, it is characterized in that, the particle diameter of described metal powder is less than 100 microns.
7. Integral load pole piece according to claim 1, is characterized in that, the capacity of described negative material is at more than 400mAh/g.
8. Integral load pole piece according to claim 1, is characterized in that, described negative material is selected from Si, Li-Si alloy, Fe
3o
4, B, Sn, SnO, black phosphorus, NiO, TiO
2and at least one in their mixture.
9. Integral load pole piece according to claim 8, is characterized in that, described negative material is Si, Li-Si alloy, B, Sn, Fe
3o
4, SnO, NiO or TiO
2.
10., according to the arbitrary described Integral load pole piece of claim 1, it is characterized in that, the particle diameter of described negative material is less than 20 microns.
11. Integral load pole pieces according to claim 1, is characterized in that, the raw material of this Integral load pole piece comprises negative material, metal powder and lithium powder, and this Integral load pole piece is suppressed by described raw material and formed.
12. Integral load pole pieces according to claim 11, is characterized in that, the particle diameter of described lithium powder is less than 200 microns.
13. Integral load pole pieces according to claim 1, is characterized in that, the raw material of this Integral load pole piece comprises negative material, metal powder, lithium powder and leads lithium ion additive, and this Integral load pole piece is suppressed by described raw material and formed.
14. Integral load pole pieces according to claim 13, is characterized in that, described in lead lithium ion additive and be selected from conductive carbon black, carbon nano-tube, Graphene, Li
4ti
5o
12, LiBO
2, Li
3pO
4, Li
nsi, Li
2s, Li
mb and Li
3at least one in N, wherein, n is 0.1 ~ 4, m is 0.1 ~ 3.
15. Integral load pole pieces according to claim 1, it is characterized in that, the raw material of this Integral load pole piece comprises negative material, metal powder, lithium powder, leads lithium ion additive and structure enhancing support material, and this Integral load pole piece is suppressed by described raw material and formed.
16. Integral load pole pieces according to claim 15, it is characterized in that, described structure enhancing support material is selected from least one in carbon cloth or carbon fibre web, high molecular polymer cloth or high molecular polymer net, porous metals sheet, porous alloy sheet, foam metal, foamed alloy, wire netting and alloy network, and described metal is do not form the metal of alloy with lithium.
17. Integral load pole pieces according to claim 16, is characterized in that, described structure strengthens support material and is selected from aramid fabric or aramid fiber net.
18. Integral load pole pieces according to claim 16, it is characterized in that, described structure enhancing support material is selected from least one in porous metals sheet and porous alloy sheet, and described metal is selected from Cu, Ag, Au and Zn, and described alloy is selected from the alloy containing Ni metal, Ag, Au or Zn.
19. Integral load pole pieces according to claim 16, it is characterized in that, described structure enhancing support material is selected from least one in foam metal and foamed alloy, and described metal is selected from Cu, Ni and Zn, and described alloy is selected from the alloy containing Ni metal, Ni or Zn.
20. Integral load pole pieces according to claim 16, it is characterized in that, described structure enhancing support material is selected from least one in wire netting and alloy network, and described metal is selected from Cu, Ni, Ag, Au and Zn, and described alloy is selected from the alloy containing Ni metal, Ni, Ag, Au or Zn.
The preparation method of 21. 1 kinds of Integral load pole pieces as claimed in claim 1, comprises the steps: 1) a kind of raw material of Integral load pole piece is provided, described raw material comprises negative material and a kind of metal powder; 2) described raw material mixing compacting is formed Integral load pole piece.
The preparation method of 22. 1 kinds of Integral load pole pieces as claimed in claim 21, is characterized in that, described raw material also comprises lithium powder.
The preparation method of 23. 1 kinds of Integral load pole pieces as claimed in claim 22, is characterized in that, described raw material also comprises leads lithium ion additive.
The preparation method of 24. 1 kinds of Integral load pole pieces as claimed in claim 23, is characterized in that, described raw material also comprises structure and strengthens support material.
25., according to the preparation method of the arbitrary described Integral load pole piece of claim 21-24, is characterized in that, described step 2) be carry out in an inert atmosphere.
26., according to the preparation method of the arbitrary described Integral load pole piece of claim 21-24, is characterized in that, described in be compressed to roll-in.
27., according to the preparation method of the arbitrary described Integral load pole piece of claim 21-23, is characterized in that, after described mixing is pressed into pole piece, carries out laser scanning sinter to obtain Integral load pole piece to pole piece.
The preparation method of 28. Integral load pole pieces according to claim 27, is characterized in that, described to pole piece carry out laser scanning sintering carry out in an inert atmosphere.
29. according to the preparation method of the arbitrary described Integral load pole piece of claim 21-23, and it is characterized in that, after described mixing is pressed into pole piece, using plasma carries out thermal sintering to pole piece and obtains Integral load pole piece.
The preparation method of 30. Integral load pole pieces according to claim 29, is characterized in that, described using plasma carries out thermal sintering to pole piece and carries out in an inert atmosphere.
The preparation method of 31. Integral load pole pieces according to claim 24, it is characterized in that, a kind of liquid dispersed agent is provided further, described raw material is added in liquid dispersed agent to mix and make slurry, described slurry being coated described structure strengthens in support material, then volatilization removing dispersant, through suppressing to obtain Integral load pole piece.
The preparation method of 32. Integral load pole pieces according to claim 31, is characterized in that, described liquid dispersed agent is selected from toluene, dimethylbenzene, the carbon number alkene between 7 to 20, the alkane of carbon number between 7 to 20 and at least one in aromatic hydrocarbons.
The preparation method of 33. Integral load pole pieces according to claim 31, is characterized in that, described liquid dispersed agent is the ether of carbon number between 7 to 20.
The preparation method of 34. Integral load pole pieces according to claim 31, it is characterized in that, described liquid dispersed agent is that paraffin is dissolved in the solution formed in alkene between 7 to 20 of toluene, dimethylbenzene, carbon number or the alkane of carbon number between 7 to 20, and wherein paraffin mass content is in the solution between 0.1% to 20%.
The preparation method of 35. Integral load pole pieces according to claim 31, is characterized in that, described liquid dispersed agent is the solution that paraffin is dissolved in carbon number and is formed in the ether of 7 to 20, and wherein paraffin mass content is in the solution between 0.1% to 20%.
36. 1 kinds of lithium ion batteries, comprise Integral load pole piece as claimed in claim 1.
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